Crosslinkable coating compositions formulated with dormant carbamate initiator

ABSTRACT

A crosslinkable coating composition comprising: ingredient A that has at least two protons that can be activated to form a Michael carbanion donor; ingredient B that functions as a Michael acceptor having at least two ethylenically unsaturated functionalities each activated by an electron-withdrawing group; and a dormant carbamate initiator of Formula (1) 
     
       
         
         
             
             
         
       
     
     wherein R 1  and R 2  can be independently selected from hydrogen, a linear or branched substituted or unsubstituted alkyl group having 1 to 22 carbon atoms; 1 to 8 carbon atoms; and A n+  is a cationic species or polymer and n is an integer equal or greater than 1 with the proviso that A n+  is not an acidic hydrogen; and optionally further comprising ammonium carbamate (H 2 NR 1 R 2   +− OC═ONR 1 R 2 ). The crosslinkable coating composition can be used for a variety of coating applications including nail coating compositions.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority benefit from U.S. Provisional PatentApplication 62/356,918 filed Jun. 30, 2016 which is incorporated byreference herein in its entirety.

FIELD OF THE INVENTION

The invention provides for a crosslinkable composition using a dormantcarbamate initiator for use in various coating compositions such as nailcoating compositions.

BACKGROUND OF THE INVENTION

The coatings industry continues to develop new chemistries asperformance requirements for decorative and functional coatings evolve.Drivers for change are varied and these can include: regulatory controlsto reduce VOC emissions, concerns about toxic hazards of coating rawmaterials, a desire for cost reduction, commitments to sustainability,and a need for increased product effectiveness.

UV nail gel coatings have gained rapid popularity with fashion consciousindividuals who apply nail polish to fingernails or toenails to decorateand protect nail plates. UV nail gels can produce coatings that exhibitphenomenal chip resistance and durability when properly applied andcured in comparison to those nail coatings derived from traditionalsolvent based nail lacquers. The performance difference particularlybecomes apparent when the coating is applied on human finger nails andtested for durability. UV nail gel coatings can easily last for twoweeks or more and still look like new whereas conventional nail polishesare easily scratched and will chip or peel from the natural nail in oneto five days. UV nail gels are typically based on acrylates that curequickly into dense, crosslinked thermoset coatings within half a minuteor so. This is an advantage as the coating becomes almost immediatelyresistant to denting and scratching. Conventional nail lacquers showsignificant sensitivity to denting while the solvent evaporates from thecoating and this requires great care by the individual as the coatingdries and hardens; a process that can take easily fifteen to twentyminutes. However, conventional nail polish is easily removed withsolvent whereas it can take some effort to remove a fully cured UV nailgel from the nail surface. An expensive UV light also is required for UVnail gel application and this has limited the success of UV nail gels inthe mass market for home use. The expense of a UV light is less of anissue for professional salons where a right balance between service rateand a customers' perception of service is more important. As such, thereis a need in the consumer market place for durable nail coatings thatcan cure quickly but do not require procurement of an UV light.

Highly crosslinked, durable coating compositions can be achieved usingMichael addition chemistry. The Michael addition reaction involves thenucleophilic addition of a Michael donor, such as a carbanion or anothernucleophile to a Michael acceptor, such as an α,β-unsaturated carbonyl.As such, the base catalyzed addition of activated methylene moieties toelectron deficient C═C double bonds are known in coatings applications.Representative examples of suitable materials that can provide activatedmethylene or methine groups are generally disclosed in U.S. Pat. No.4,871,822, which resins contain a methylene and/or monosubstitutedmethylene group in the alpha-position to two activating groups such as,for example, carbonyl, cyano, sulfoxide and/or nitro groups. Preferredare resins containing a methylene group in the alpha-position to twocarbonyl groups, such as malonate and/or acetoacetate group-containingmaterials, malonates being most preferred. The α,β-unsaturated carbonyltypically is an acrylate material and representative materials have beendisclosed in U.S. Pat. No. 4,602,061. The Michael reaction is fast, canbe carried out at ambient temperatures and gives a chemically stablecrosslinking bond without forming any reaction by-product.

A typical crosslinkable coating composition comprises a resin ingredientA (Michael donor), a resin ingredient B (Michael acceptor) and a base tostart and catalyze the Michael addition reaction. The base catalystshould be strong enough to abstract, i.e. activate a proton from resiningredient A to form the Michael donor carbanion species. Since theMichael addition cure chemistry can be very fast, the coating formulatoris challenged to control the speed of the reaction to achieve anacceptable balance of pot life, open time, tack free time and cure time.Pot life is defined as the amount of time during which the viscosity ofa mixed reactive system doubles. Working life or working time informsthe user how much time they have to work with a reactive two part systembefore it reaches such a high state of viscosity, or other condition,that it cannot be properly worked with to produce an acceptableapplication result. Gel time is the amount of time it takes for a mixed,reactive resin system to gel or become so highly viscous that it haslost fluidity. The open time of a coating is a practical measure of howmuch time it takes for a drying or curing coating to reach a stage whereit can no longer be touched by brush or roller when applying additionalcoating material without leaving an indication that the drying or curingcoating and newly applied coating did not quite flow together. Theseindications normally take the form of brush or roller marks andsometimes a noticeable difference in sheen levels. The tack free time isthe amount of time it takes for a curing or drying coating to be nolonger sticky to the touch, i.e. the time for a system to become hard tothe touch, with no tackiness. Cure time is the amount of time it takesfor a coating system to reach full final properties.

The Michael reaction starts the very moment when coating resiningredients A and B are mixed together with a suitable base. Since it isa fast reaction, the material in a mixing pot starts to crosslink andthe fluid viscosity starts to rise. This limits the pot life, workingtime and general use as a coating. A dormant initiator that isessentially passive while coating material remains in a mixing vesselbut that activates the Michael addition reaction upon film formationallows for longer pot life and working time, yet would show good opentime, tack free time and cure time. Hence, the application of dormantinitiator technology can provide the formulator with tools to controlthe speed of the reaction in order to achieve desirable curecharacteristics.

U.S. Pat. No. 8,962,725 describes a blocked base catalyst for Michaeladdition, which is based on substituted carbonate salts. PreferredMichael donor resins are based on malonate and Michael acceptor resinsare acrylates. The substituted carbonates can bear substituents, butthese should not substantially interfere with the crosslinking reactionbetween malonate and acrylate. The carbonate salts release carbondioxide and a strong base upon activation by means of film formation.The base is either hydroxide or alkoxide. Before practical pot life andgel times are achieved with acceptable curing characteristics, thecarbonate requires presence of a certain amount of water in the coatingformulation for the blocking of the base to become effective. Alldisclosed blocked carbonate examples utilize methanol and/or water.However, malonate esters are known to be susceptible to base hydrolysis,particularly when water is present. Hence, the water necessary to blockthe carbonate base can thus degrade malonate oligomers or polymers atthe same time, which in turn can lead to altered coatings performance.The hydrolysis product furthermore can result in undesirable destructionof base catalyst by means of formation of malonate salt; a reactionwhich is cloaked as longer pot life and gel time. Presence of water canalso be quite problematic in certain coatings applications. Wood grainraising is a significant problem when water is present in wood coatings;water penetrates into wood, which causes swelling and lifting of fibersand this leaves a rough surface. Water also can cause flash rust, i.e.appearance of rust spots on a metal surface during drying of newlyapplied paint that contains water. Longer term rust formation in termsof corrosion may also be a problem when dealing with formulations thatcontain water.

SUMMARY OF THE INVENTION

In one embodiment, the present invention provides for a crosslinkablecoating composition comprising: ingredient A that has at least twoprotons that can be activated to form a Michael carbanion donor;ingredient B that functions as a Michael acceptor having at least twoethylenically unsaturated functionalities each activated by anelectron-withdrawing group; and a dormant carbamate initiator of Formula(1)

wherein R₁ and R₂ can be independently selected from hydrogen, a linearor branched substituted or unsubstituted alkyl group having 1 to 22carbon atoms; 1 to 8 carbon atoms; and A^(n+) is a cationic species orpolymer and n is an integer equal or greater than 1 with the provisothat A^(n+) is not an acidic hydrogen; and optionally further comprisingammonium carbamate (H₂NR₁R₂ ⁺⁻OC═ONR₁R₂). In one such embodiment, thedormant carbamate initiator initiates Michael Addition to achieve crosslinking when the crosslinkable coating composition is applied to asurface.

In another embodiment, the present invention provides for thecrosslinkable coating composition wherein ingredient A is selected fromthe group consisting of compounds, oligomers or polymers. In one suchembodiment, the present invention provides for crosslinkable coatingcomposition wherein the ingredient A is independently selected from amalonate group containing compound, a malonate group containingoligomer, a malonate group containing polymer, an acetoacetate groupcontaining compound, an acetoacetate group containing oligomer, anacetoacetate group containing polymer or combinations thereof.

In one such embodiment, the present invention provides for thecrosslinkable coating composition wherein the malonate group containingcompound, malonate group containing oligomer, malonate group containingpolymer, an acetoacetate group containing compound, acetoacetate groupcontaining oligomer, or acetoacetate group containing polymer are eachselected from the group consisting of: polyurethanes, polyesters,polyacrylates, epoxy polymers, polyamides, polyesteramides or polyvinylpolymers, wherein such compounds, oligomers or polymers have (i) amalonate group; (ii) an acetoacetate group or (iii) combinations thereoflocated in a main chain of such compound or oligomer or polymer or aside chain of such compound or oligomer or polymer.

In another embodiment, the present invention provides for thecrosslinkable coating composition wherein ingredient B is selected fromthe group consisting of acrylates, fumarates, maleates and combinationsthereof. In one such embodiment, the present invention provides for thecrosslinkable coating composition wherein the acrylate is independentlyselected from the group consisting of hexanediol diacrylate,trimethylolpropane triacrylate, pentaerythritol triacrylate,di-trimethylolpropane tetraacrylate, bis(2-hydroxyethyl acrylate)trimethylhexyl dicarbamate, bis(2-hydroxyethyl acrylate)1,3,3-trimethylcyclohexyl dicarbamate, bis(2-hydroxyethyl acrylate)methylene dicyclohexyl dicarbamate and combinations thereof.

In one such embodiment, the present invention provides for thecrosslinkable coating composition wherein ingredient B is independentlyselected from polyesters, polyurethanes, polyethers and/or alkyd resinseach containing at least two pendant ethylenically unsaturated groupseach activated by an electron-withdrawing group.

In one such embodiment, the present invention provides for thecrosslinkable coating composition wherein ingredient B is independentlyselected from the group consisting of polyesters, polyurethanes,polyethers and/or alkyd resins each containing at least one pendantacryloyl functional group.

In another embodiment, the present invention provides for thecrosslinkable coating composition further comprising an ingredient Dhaving one or more reactive protons that are more acidic than theprotons of ingredient A, with respect to pKa. In one such embodiment,the present invention provides for the crosslinkable coating compositionwherein the one or more reactive protons of ingredient D are less acidicthan the ammonium cation of the optional ammonium carbamate, withrespect to pKa.

In another embodiment, the present invention provides for thecrosslinkable coating composition further comprising less than 10 wt. %;5 wt. %; 1 wt. %; 0.1 wt. %; 0.01 wt. % water. In another embodiment,the present invention provides for the crosslinkable coating compositionsubstantially free of water.

In another embodiment, the present invention provides for thecrosslinkable coating composition further comprising an organic solvent.In one such embodiment, the organic solvent is independently selectedfrom an alcohol, ester, ether, glycol ether, ketone, aromatic andcombinations thereof. In one such embodiment, the alcohol isindependently selected from methanol, ethanol, iso-propanol, butanol,iso-butanol and combinations thereof.

In another embodiment, the present invention provides for thecrosslinkable coating composition wherein A^(+n) is a monovalentquaternary ammonium compound of Formula (2)

wherein R₃, R₄ and R₅ are independently selected from linear or branchedalkyl chains having from 1 to 22 carbon atoms; or 1 to 8 carbon atomsand combinations thereof; and wherein R₆ is independently selected fromthe group consisting of: methyl, an alkyl group having from 2 to 6carbon atoms or a benzyl group.

In another embodiment, the present invention provides for thecrosslinkable coating composition wherein ingredient A, ingredient B andthe carbamate initiator are contained in a container having two or morechambers, which are separated from one another. In one such embodiment,ingredient A and ingredient B are contained in separate chambers toinhibit any reaction. In another such embodiment, the carbamateinitiator is contained in the chamber having ingredient A, andoptionally containing CO₂ and/or ammonium carbamate. In another suchembodiment, the carbamate initiator is contained in the chamber havingingredient B, and optionally containing CO₂ and/or ammonium carbamate.

In another embodiment, the present invention provides for thecrosslinkable coating composition such that ingredient A and ingredientB are contained in the same chamber and the carbamate initiator iscontained in a separate chamber to inhibit any reaction and saidseparate chamber optionally containing CO₂ and/or ammonium carbamate.

In another embodiment, the present invention provides for thecrosslinkable coating composition wherein ingredient A and ingredient Band carbamate initiator are contained in a container having a singlechamber, wherein the container optionally independently (i) contains CO₂and/or ammonium carbamate or (ii) contains ammonium carbonate and isfilled to capacity with essentially no space remaining for other solid,liquid or gaseous ingredients.

In another embodiment, the present invention provides for apolymerizable nail coating composition comprising the crosslinkablecoating composition described herein. In one such embodiment, thepolymerizable nail coating composition includes at least one solventselected from acetone, ethyl acetate, butyl acetate, isopropyl alcohol,ethanol, methyl ethyl ketone, and combinations thereof. In anothercertain embodiment, the polymerizable nail coating composition furtherincludes one or more of dyes, pigments, effect pigments, phosphorescentpigments, flakes and fillers and combinations thereof. In anothercertain embodiment, the polymerizable nail coating composition furtherincludes a rheological additive to modify rheology. In another certainembodiment, the polymerizable nail coating composition further includesa wetting agent. In another embodiment, the polymerizable nail coatingcomposition further includes an adhesion promotor. In another certainembodiment, the polymerizable nail coating composition includesnitrocellulose, polyvinylbutyral, tosylamide formaldehyde and/ortosylamide epoxy resins. In another certain embodiment, thepolymerizable nail coating composition includes a cellulose acetatealkylate selected from the group consisting of cellulose acetatebutyrate, cellulose acetate propionate, and mixtures thereof. In anothercertain embodiment, the polymerizable nail coating composition includesat least one colorant independently selected from the group consistingof (i) a dye; (ii) an inorganic pigment; (iii) a lake or (iv)combinations thereof.

In another embodiment, the present invention provides for a coatingcomposition comprising the crosslinkable coating composition asdescribed herein.

In another embodiment, the present invention provides for acrosslinkable coating composition comprising: ingredient A that has atleast two protons that can be activated to form a Michael carbaniondonor; ingredient B that functions as a Michael acceptor having at leasttwo ethylenically unsaturated functionalities each activated by anelectron-withdrawing group; and ingredient C, which is a dormantcarbamate initiator system formed from: a: ammonium carbamate saltderived from the reaction of: a1: carbon dioxide a2: one or morepolyamines a3: optionally one or more monoamines b: such ammoniumcarbamate salt being subsequently treated with base, ion exchange orother chemical means so that at least part of the protonated ammoniumcations have been replaced by A^(n+), and where A^(n+) is a cationicspecies or polymer and n is an integer equal or greater than 1 with theproviso that A^(n+) is not hydrogen.

DETAILED DESCRIPTION

The invention disclosed here is a crosslinkable composition comprising aresin ingredient A (Michael donor), a resin ingredient B (Michaelacceptor) and a dormant carbamate initiator ingredient C. The inventiongenerally is useful as a decorative and/or functional coating, and theinvention particularly is useful as a coating for human finger nails ortoe nails.

Resin Ingredient A (Michael Donor):

Resin ingredients A are compounds, oligomers or polymers that containfunctional groups that have reactive protons that can be activated toproduce a carbanion Michael donor. In one embodiment, the functionalgroup can be a methylene or methine group and resins have been describedin U.S. Pat. No. 4,602,061 and U.S. Pat. No. 8,962,725 for example. Inone embodiment, resin ingredients A are those derived from malonic acidor malonate esters, i.e. malonate. Oligomeric or polymeric malonatecompounds include polyurethanes, polyesters, polyacrylates, epoxyresins, polyamides, polyesteramides or polyvinyl resins each containingmalonate groups, either in the main chain or the side chain or in both.

In one embodiment, polyurethanes having malonate groups may be obtained,for instance, by bringing a polyisocyanate into reaction with a hydroxylgroup containing ester or polyester of a polyol and malonicacid/malonates, by esterification or transesterification of a hydroxylfunctional polyurethane with malonic acid and/or a dialkyl malonate.Examples of polyisocyanates include hexamethylenediisocyanate,trimethylhexamethylene diisocyanate, isophorone diisocyanate, toluenediisocyanate and addition products of a polyol with a diisocyanate, suchas that of trimethylolpropane to hexamethylene diisocyanate. In oneembodiment, the polyisocyanate is selected from isophorone diisocyanateand trimethyhexamethylene diisocyanate. In another embodiment, thepolyisocyanate is isophorone diisocyanate. In some embodiments, hydroxylfunctional polyurethanes include the addition products of apolyisocyanate, such as the foregoing polyisocyanates, with di- orpolyvalent hydroxyl compounds, including diethyleneglycol, neopentylglycol, dimethylol cyclohexane, trimethylolpropane, 1,3-propandiol,1,4-butanediol, 1,6-hexanediol and polyether polyols, polyester polyolsor polyacrylate polyols. In some embodiments, the di- or polyvalenthydroxyl compounds include diethyleneglycol, 1,3-propanediol,1,4-butanediol and 1,6-hexanediol. In other embodiments, the di- orpolyvalent hydroxyl compounds include diethyleneglycol and1,6-hexanediol.

In one embodiment, malonic polyesters may be obtained, for instance, bypolycondensation of malonic acid, an alkylmalonic acid, such asethylmalonic acid, a mono- or dialkyl ester of such a carboxylic acid,or the reaction product of a malonic ester and an alkylacrylate ormethacrylate, optionally mixed with other di- or polycarboxylic with oneor more dihydroxy and/or polyhydroxy compounds, in combination or notwith mono hydroxyl compounds and/or carboxyl compounds. In someembodiments, polyhydroxy compounds include compounds containing 2-6hydroxy group and 2-20 carbon atoms, such as ethylene glycol,diethyleneglycol, propylene glycol, trimethylol ethane,trimethylolpropane, glycerol, pentaerythritol, 1,4-butanediol,1,6-hexanediol, cyclohexanedimethanol, 1,12-dodecanediol and sorbitol.In some embodiments, the polyhydroxy compounds include diethyleneglycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol. In otherembodiments, the polyhydroxyl compounds include propylene glycol and1,6-hexanediol. In certain embodiments, the polyhydroxy may be a primaryalcohol and in certain other embodiments, the polyhydroxy may be asecondary alcohol. Examples of polyols with secondary alcohol groups are2,3-butanediol, 2,4-pentanediol and 2,5-hexanediol and the like.

In one embodiment, malonate group-containing polymers also may beprepared by transesterification of an excess of dialkyl malonate with ahydroxyl functional polymer, such as a vinyl alcohol-styrene copolymer.In this way, polymers with malonate groups in the side chains areformed. After the reaction, the excess of dialkyl malonate mayoptionally be removed under reduced pressure or be used as reactivesolvent.

In one embodiment, malonate group or acetoacetate group containingpolymers may also be obtained from reaction with malonate oracetoacetonate with polyols, such as those polyols that are commerciallysold for reaction with isocyanates to form polyurethane coatings.

In one embodiment, malonic epoxy esters may be prepared by esterifyingan epoxy polymer with malonic acid or a malonic monoester, or bytransesterifying with a dialkylmalonate, optionally in the presence ofone or more other carboxylic acids or derivatives thereof.

In one embodiment, polyamides having malonate groups may be obtained inthe same manner as polyesters, at least part of the hydroxyl compound(s)being replaced with a mono- or polyvalent primary and/or secondaryamine, such as cyclohexylamine, ethylene diamine, isophorone diamine,hexamethylene diamine, or diethylene triamine.

In some embodiments, such polyamide compounds can be obtained when12-hydroxystearic acid is reacted with a diamine such asethylenediamine. Such polyamides have secondary alcohol groups, whichcan be esterified with malonic acid or malonate in a second reactionstep. In some embodiments, other diamines may also be used in thereaction with 12-hydroxystearic acid, for example: xylylenediamine,butylenediamine, hexamethylenediamine, dodecamethylenediamine, and evendimer amine, which is derived from dimer acid. Polyamines may also beused, but in a right stoichiometric ratio as to avoid gelling of thepolyamide in the reactor. Lesquerolic acid may also be used in reactionswith polyamines to yield polyamides bearing secondary alcohol groups,which can be used in reactions with malonate to form malonate containingcompounds. Reactions that yield malonamides are much less desirable.

In some embodiments, the above mentioned malonate resins may be blendedtogether to achieve optimized coatings properties. Such blends can bemixtures of malonate modified polyurethanes, polyesters, polyacrylates,epoxy resins, polyamides, polyesteramides and the like, but mixtures canalso be prepared by blending various malonate modified polyesterstogether. In some other embodiments, various malonate modifiedpolyurethanes can be mixed together, or various malonate modifiedpolyacrylates, or malonate modified epoxy resins, or various malonatemodified polyamides, malonate modified polyesteramides.

In certain embodiments, malonate resins are malonate group containingoligomeric esters, polyesters, polyurethanes, or epoxy esters having1-100, or 2-20 malonate groups per molecule. In some such embodiments,the malonate resins should have a number average molecular weight in therange of from 250 to 10,000 and an acid number not higher than 5, or nothigher than 2. Use may optionally be made of malonate compounds in whichthe malonic acid structural unit is cyclized by formaldehyde,acetaldehyde, acetone or cyclohexanone. In some embodiments, molecularweight control may be achieved by the use of end capping agents,typically monofunctional alcohol, monocarboxylic acid or esters. In oneembodiment, malonate compounds may be end capped with one or more of1-hexanol, 1-octanol, 1-dodecanol, hexanoic acid or its ester, octanoicacid or its esters, dodecanoic acid or its esters, diethyleneglycolmonoethyl ether, trimethylhexanol, and t-butyl acetoacetate, ethylacetoacetate. In one such embodiment, the malonate is end capped with1-octanol, diethyleneglycol monoethyl ether, trimethylhexanol, t-butylacetoacetate and ethyl acetoacetate. In another such embodiment, themalonate is end capped t-butyl acetoacetate, ethyl acetoacetate andcombinations thereof.

Monomeric malonates may optionally be used as reactive diluents, butcertain performance requirements may necessitate removal of monomericmalonates from resin ingredient A.

In some embodiments, resin ingredients A include oligomeric and/orpolymeric acetoacetate group-containing resins. In some embodiments,such acetoacetate group-containing resins are acetoacetic esters asdisclosed in U.S. Pat. No. 2,759,913, diacetoacetate resins as disclosedin U.S. Pat. No. 4,217,396 and acetoacetate group-containing oligomericand polymeric resins as disclosed in U.S. Pat. No. 4,408,018. In someembodiments, acetoacetate group-containing oligomeric and polymericresins can be obtained, for example, from polyalcohols and/orhydroxyl-functional polyether, polyester, polyacrylate, vinyl and epoxyoligomers and polymers by reaction with diketene or transestericationwith an alkyl acetoacetate. Such resins may also be obtained bycopolymerization of an acetoacetate functional (meth)acrylic monomerwith other vinyl- and/or acrylic-functional monomers. In certain otherembodiments, the acetoacetate group-containing resins for use with thepresent invention are the acetoacetate group-containing oligomers andpolymers containing at least 1, or 2-10, acetoacetate groups. In somesuch embodiments, such acetoacetate group containing resins should haveMn in the range of from about 100 to about 5000 g/mol, and an acidnumber of about 2 or less. Resins containing both malonate andacetoacetate groups in the same molecule may also be used.

In another embodiment, the above mentioned malonate group containingresins and acetoacetate group-containing resins may also be blended tooptimize coatings properties as desired, often determined by theintended end application.

Structural changes at the acidic site of malonate or acetoacetate canalter the acidity of these materials and derivatives thereof. Forinstance, pKa measurements in DMSO show that diethyl methylmalonate(MeCH(CO₂Et)₂) has a pKa of 18.7 and diethyl ethylmalonate(EtCH(CO₂Et)₂) has a pKa of 19.1 whereas diethyl malonate (CH₂(CO₂Et)₂)has a pKa of 16.4. Resin ingredient A may contain such substitutedmoieties and therewith show changes in gel time, open time, cure timeand the like. For example, resin ingredient A may be a polyester derivedfrom a polyol, diethyl malonate and diethyl ethylmalonate.

Resin Ingredient B (Michael Acceptor):

Resin ingredients B (Michael acceptor) generally can be materials withethylenically unsaturated moieties in which the carbon-carbon doublebond is activated by an electron-withdrawing group, e.g. a carbonylgroup in the alpha-position. In some embodiments, resin ingredients Bare described in: U.S. Pat. No. 2,759,913, U.S. Pat. No. 4,871,822, U.S.Pat. No. 4,602,061, U.S. Pat. No. 4,408,018, U.S. Pat. No. 4,217,396 andU.S. Pat. No. 8,962,725. In certain embodiments, resin ingredients Binclude acrylates, fumarates and maleates. In other certain embodiments,resin ingredient B is an unsaturated acryloyl functional resin.

In some embodiments, resin ingredients B are the acrylic esters ofchemicals containing 2-6 hydroxyl groups and 2-20 carbon atoms. Theseesters may optionally contain hydroxyl groups. In some such embodiments,examples of such acrylic esters include hexanediol diacrylate,trimethylolpropane triacrylate, pentaerythritol triacrylate,di-trimethylolpropane tetraacrylate. In one such embodiment, acrylicesters include trimethylolpropane triacrylate, di-trimethylolproanetetraacrylate, dipentaerythritol hexaacrylate, pentaerythritolethoxylated (EO)_(n) tetraacrylate, trimethylolpropaneethoxylated(EO)_(n) triacrylate and combinations thereof. In anotherembodiment, acrylamides may be used as a resin ingredient B.

In other embodiments, resin ingredients B are polyesters based uponmaleic, fumaric and/or itaconic acid (and maleic and itaconicanhydride), and chemicals with di- or polyvalent hydroxyl groups,optionally including materials with a monovalent hydroxyl and/orcarboxyl functionality.

In other embodiments, resin ingredients B are resins such as polyesters,polyurethanes, polyethers and/or alkyd resins containing pendantactivated unsaturated groups. These include, for example, urethaneacrylates obtained by reaction of a polyisocyanate with an hydroxylgroup-containing acrylic ester, e.g., an hydroxyalkyl ester of acrylicacid or a resins prepared by esterification of a polyhydroxyl materialwith acrylic acid; polyether acrylates obtained by esterification of anhydroxyl group-containing polyether with acrylic acid; polyfunctionalacrylates obtained by reaction of an hydroxyalkyl acrylate with apolycarboxylic acid and/or a polyamino resin; polyacrylates obtained byreaction of acrylic acid with an epoxy resin; and polyalkylmaleatesobtained by reaction of a monoalkylmaleate ester with an epoxy polymerand/or an hydroxyl functional oligomer or polymer. In certainembodiments, polyurethane acrylate resins may be prepared by reaction ofhydroxyalkyl acrylate with polyisocyanate. Such polyurethane acrylateresins independently include bis(2-hydroxyethyl acrylate) trimethylhexyldicarbamate [2-hydroxyethyl acrylate trimethylhexamethylene diisocyanate(TMDI) adduct], bis(2-hydroxyethyl acrylate) 1,3,3-trimethylcyclohexyldicarbamate [2-hydroxyethylacrylate 1,3,3-trimethylcyclohexyldiisocyanate/isophorone diisocyanate (IPDI) adduct], bis(2-hydroxylethylacrylate) hexyl dicarbamate [2-hydroxyethyl acrylate hexamethylenediisocyanate (HDI) adduct], bis(2-hydroxylethyl acrylate) methylenedicyclohexyl dicarbamate [2-hydroxyethyl acrylate methylene dicyclohexyldiisocyanate (HMDI) adduct], bis(2-hydroxyethyl acrylate)methylenediphenyl dicarbamate [2-hydroxyethylacrylate methylenediphenyldiisocyanate (MDI) adduct], bis(4-hydroxybutyl acrylate)1,3,3-trimethylcyclohexyl dicarbamate [4-hydroxybutyl acrylate IPDIadduct], bis(4-hydroxybutyl acrylate) trimethylhexyl dicarbamate[4-hydroxybutyl acrylate TMDI adduct], bis(4-hydroxybutyl acrylate)hexyl dicarbamate [4-hydroxybutyl acrylate HDI adduct],bis(4-hydroxybutyl acrylate) methylene dicyclohexyl dicarbamate[4-hydroxybutyl acrylate HMDI adduct], bis(4-hydroxybutyl acrylate)methylenediphenyl dicarbamate [4-hydroxybutyl acrylate MDI adduct].

In other embodiments, resin ingredients B have unsaturated acryloylfunctional groups.

In certain embodiments, the acid value of the activated unsaturatedgroup-containing material (resin ingredient B) is sufficiently low tonot substantially impair the Michael addition reaction, for example lessthan about 2, and further for example less than 1 mg KOH/g.

As exemplified by the previously incorporated references, these andother activated unsaturated group containing resins, and their methodsof production, are generally known to those skilled in the art, and needno further explanation here. In certain embodiments, the number ofreactive unsaturated group ranges from 2 to 20, the equivalent molecularweight (EQW: average molecular weight per reactive functional group)ranges from 100 to 2000, and the number average molecular weight Mnranges from 100 to 5000.

In one embodiment, the reactive part of resin ingredients A and B canalso be combined in one A-B type molecule. In this embodiment of thecrosslinkable composition both the methylene and/or methine features aswell as the α,β-unsaturated carbonyl are present in the same molecule,be it a monomer, oligomer or polymer. Mixtures of such A-B typemolecules with ingredient A and B are also useful.

Each of the foregoing embodiments of resin ingredient A and resiningredient B may be combined with the various embodiments of a dormantcarbamate initiator ingredient C, described below, to arrive at theinventions described herein. In one embodiment, resin ingredient A is apolyester malonate composition and resin ingredient B is a polyesteracrylate. In another embodiment, resin ingredient A is a polyurethanemalonate composition and resin ingredient B is a polyester acrylate. Inanother embodiment, resin ingredient A is a polyurethane malonatecomposition and resin ingredient B is a polyester acrylate. In anotherembodiment, resin ingredient A is a polyurethane malonate compositionand resin ingredient B is a polyurethane acrylate. In anotherembodiment, resin ingredient A is a polyester malonate havingacetoacetate end groups and resin ingredient B is a polyester acrylate.In yet another embodiment, resin ingredient A is a polyester malonatehaving acetoacetate end groups and resin ingredient B is a polyurethaneacrylate. In still yet another embodiment, resin ingredient A is apolyester malonate having acetoacetate end groups and resin ingredient Bis a mixture of polyester acrylate and polyurethane acrylate.

In the foregoing embodiments, the number of reactive protons for resiningredients A, and the number of α,β-unsaturated carbonyl moieties onresin ingredient B can be utilized to express desirable ratios andranges for resin ingredients A and B. Typically, the mole ratio ofreactive protons of ingredient A that can be activated with subsequentcarbanion formation relative to the activated unsaturated groups oningredient B is in the range between 10/1 and 0.1/1, or between 4/1 and0.25/1, or between 3.3/1 and 0.67/1. However, the optimal amountstrongly depends also on the number of reactive groups present oningredients A and/or B.

The amount of dormant carbamate initiator used, expressed as mole ratioof protons that can be abstracted to form an activated Michael donorspecies (e.g. the methylene group of malonate can provide two protonsfor reactions, while a methine group can provide one proton to form anactivated species) relative to initiator, ranges from about 1000/1 to1/1, or from 250/1 to 10/1, or from 125/1 to 20/1 but the optimal amountto be used depends also on the amount of solvent present, reactivity ofvarious acidic protons present on resin ingredients A and/or B.

Dormant Carbamate Initiator Ingredient C:

Ingredient C is a dormant carbamate initiator with a structure shown inFormula 1:

R₁ and R₂ can be independently selected and is hydrogen or an alkylgroup with 1 to 22 carbon atoms where the alkyl group can be linear orbranched. In some embodiments, the alkyl group has 1 to 8 carbon atomsor the alkyl group has 1 to 4 carbon atoms. In some such embodiments,the alkyl group is selected from a methyl group, ethyl group, propylgroup, butyl group and combinations thereof. In certain embodiments, thealkyl groups are unsubstituted alkyl groups. In other embodiments, thealkyl group can be substituted. In certain embodiments, both R₁ and R₁are substituted with hydroxyl groups. A^(n+) is a cationic material andn is an integer equal or greater than 1, with the proviso that A^(n+) isnot an acidic hydrogen. In some embodiments, A^(n+) can be a monovalentcation, such as an alkali metal, earth alkali metal or anothermonovalent metal cation, a quaternary ammonium, a sulfonium or aphosphonium compound. In some embodiments, A^(n+) can also be amultivalent metal cation, or a compound bearing more than one quaternaryammonium or phosphonium groups, or can be a cationic polymer. In certainembodiments, A^(n+) is a monovalent quaternary ammonium cation where nis 1. For the various embodiments described herein, dormant carbamateinitiator ingredient C is significantly slow in promoting the Michaelreaction prior to applying the crosslinkable composition of thisinvention as a coating so it can be regarded as essentially inactive, orminimally active, while in a container, yet the initiator initiatesMichael addition reaction once the coating is applied as a film.

In some embodiments, the dormant carbamate initiator is derived fromcarbamates, (H₂NR₁R₂ ⁺⁻OC═ONR₁R₂), independently selected from ammoniumcarbamate, methylammonium methylcarbamate, ethylammonium ethylcarbamate,propylammonium propylcarbamate, isopropylammonium isopropylcarbamate,butylammonium butylcarbamate, isobutylammonium isobutylcarbamate,pentylammonium pentylcarbamate, and hexylammonium hexylcarbamate. Inother embodiments, the dormant carbamate initiator is derived fromcarbamates independently selected from dimethylammoniumdimethylcarbamate, diethylammonium diethylcarbamate, dipropylammoniumdipropylcarbamate, dibutylammonium dibutylcarbamate, diisobutylammoniumdiisobutylcarbamate, dipentylammonium dipentylcarbamate, dihexylammoniumdihexylcarbamate, and dibenzylammonium dibenzylcarbamate. In otherembodiments, the dormant carbamate initiator is derived from carbamatesindependently selected from N-methylethylammonium methylethylcarbamate,N-methylpropylammonium methylpropylcarbamate, and N-methylbenzylammoniummethylbenzylcarbamate. In some certain embodiments, the dormantcarbamate initiator is derived from carbamates independently selectedfrom dimethylammonium dimethylcarbamate, diethylammoniumdiethylcarbamate, dipropylammonium dipropylcarbamate,N-methylethylammonium methylethylcarbamate, and N-methylpropylammoniummethylpropylcarbamate.

For the various embodiments of dormant carbamate initiator, describedherein, the dormant carbamate initiator releases carbon dioxide andammonia or an amine upon activating resin ingredient A by means of ashift in equilibrium. The invention is not meant to be limited by theoryhowever, the overall activation equilibrium reaction can be envisionedas illustrated in equation 1 for example with a malonate material (R′and R″ can be the same or different and can be an alkyl or a malonatecontaining polymer). The activation process produces the carbanionMichael donor.

The carbanion can react with the Michael acceptor, an acrylate forexample, to yield a malonate-acrylate adduct, which is very basic and isreadily protonated, typically by another malonate methylene or methinemoiety thus restarting another cycle and continuing the Michael additionprocess. Solvent potentially can participate in the Michael additioncycle. The equilibrium of equation 1 can be shifted according to LeChâtelier's principle when ammonia or amine and carbon dioxide areallowed to leave the system therewith unleashing the Michael additionreaction. However, the carbon dioxide and the ammonia or amine that areformed in equation 1 react exothermally with each other at a fast rateto form an ammonium carbamate in an equilibrium reaction that favorsformation of the ammonium carbamate. This equilibrium reaction is shownin equation 2.

The protonated ammonium cation is a more acidic species (pK_(a)≈9) thanthe malonate methylene group (pK_(a)≈13) and reacts with a carbanionsuch as the malonate-acrylate adduct or the Michael donor carbanion ofingredient A for example. Unless indicated otherwise, the pKa valuesdescribed herein are defined on an aqueous basis. The initial carbamateinitiator reforms in this reaction step. This process is illustrated inequation 3, where [Mal-Ac] is the malonate acrylate adduct.

The dormant carbamate initiator thus is able to start the Michaeladdition cycle by means of a shift in equilibrium, but its decompositionproducts push back on the equilibrium and can react and stop the Michaelreaction and regenerate the dormant carbamate initiator as long as amineand carbon dioxide are available. This ensures long pot life and geltime of the coating composition. Once the coating composition is appliedon a substrate, the amine and carbon dioxide can escape into theatmosphere above the coating film and therewith unleash the full speedpotential of the Michael addition reaction.

Only ammonia, primary and secondary amines can react with carbon dioxideto form ammonium carbamate material. Tertiary amines do not react withcarbon dioxide to form carbamates. However, ammonia, and amines can alsoreact with acrylates at ambient conditions albeit at different rates andthese competing aza-Michael additions are illustrated in equation 4.

The inventors surprisingly found the carbamate initiator of formula 1 tobe dormant in the crosslinkable composition of this invention despitethe reaction shown in equation 4, which has the potential to drive ashift in equilibria. The reactions shown in equation 1, 2, 3 and 4 canbe utilized to fine tune overall pot life, open time, cure rate and geltime. The reaction shown in equation 4 has an advantage in that it canremove undesirable amine odor from the curing coating as the dormantcarbamate initiator activates.

In some embodiments, additional amine functional groups can optionallybe added to the coating formulation to impact pot life, open time, curerate and gel time. In another embodiment, both a quaternary ammoniumcarbamate, (A⁺⁻OC═ONR₁R₂), as well as an ammonium carbamate, (H₂NR₁R₂⁺⁻OC═ONR₁R₂), may be used together as a dormant initiator system. In yetanother embodiment, excess carbon dioxide may be utilized to influenceequilibria according to Le Châtelier's principle and thus influence potlife, open time, cure time and the like.

Another surprising result of this invention involves the dormantcarbamate initiator and its interaction with acetoacetylated resins.Dormancy is preserved despite the fact that amines rapidly react withacetoacetic esters to yield a resin with enamine functionalities.Enamine and ketamines are tautomers. The two isomers readilyinterconvert with each other, with the equilibrium shifting depending onthe polarity of the solvent/environment. Without being bound by theory,it is hypothesized that the enamine and ketamine groups convey increasedmethine/methylene acidity and the resin can crosslink in a reaction withα,β-unsaturated resins via Michael addition but the reactivity dependson the enamine/ketamine equilibrium. However, once the dormant carbamateinitiator actives upon film formation and releases amine and carbondioxide, the amine may preferentially react with acrylate oracetoacetate moieties in competing reactions, and thus significantlyalter the crosslinking reaction characteristics during these initialstages when amine becomes available. The coating formulator thus hasadditional tools available by making use of the rich reaction chemistrythat the amine offers by, for instance, using a mix of acetoacetate andmalonate functional groups.

In some embodiments, the crosslinkable composition of this inventioncontains some solvent. The coating formulator may choose to use analcohol, or a combination of alcohols as solvent for a variety ofreasons. This is not a problem for the carbamate initiator, andregeneration thereof, because ammonia as well as primary and secondaryamines react much faster with carbon dioxide than hydroxides or alkoxyanions. Other solvents like ethyl acetate or butyl acetate may also beused, potentially in combination with alcohol solvents. In oneembodiment ethanol or Isopropyl alcohol is the solvent. Methanol is notpreferred as a solvent because of health and safety risks, and isparticularly not preferred and cannot be used when the crosslinkablecomposition is used as a coating for finger nails and toe nails. Otheroxygenated, polar solvents such as ester or ketones for instance, can beused, potentially in combination with alcohol. Other organic solventsmay also be used. The crosslinkable composition of this invention mayalso be formulated without solvent in some cases. The crosslinkablecoating contains typically at least 5 wt. % of solvent, or between 5 wt.% and 45 wt. %, or between 5 wt. % and 35 wt. % or not more than 60 wt.% because of VOC restrictions.

In one embodiment, the crosslinkable coating composition furthercomprising less than 10 wt. %; 5 wt. %; 1 wt. %; 0.1 wt. %; 0.01 wt. %water. In such embodiments, water may be present in the solvent, eitherdeliberately added, or produced in situ in minor quantities duringpreparation of the dormant initiator. In another embodiment, thecrosslinkable coating composition is substantially free of water.

The embodiments of dormant carbamate initiator, described herein, may beprepared in various ways. In one embodiment, the dormant carbamateinitiator is prepared by ion exchange. In this embodiment, a cationexchange column is charged with quaternary ammonium ions, which in turncan replace the protonated amine of an ammonium carbamate so that aquaternary ammonium carbamate solution is obtained. In a certainembodiment, a concentrated solution of tributylmethylammonium chloridein water is passed through a cation exchange column. Next, the column iswashed free of excess salt and rinsed with anhydrous alcohol to removeany residual water. In a next step, dimethylammonium dimethylcarbamate,NH₂(CH₃)₂ ⁺⁻OC═ON(CH₃)₂, optionally diluted with alcohol, is passedthrough the column so as to obtain a tributylmethylammoniumdimethylcarbamate solution in alcohol. A similar approach with anionicion exchange columns may be devised. The solution can be titrated withbase or acid to assess the initiator concentration and whether thedormant initiator formation has been successful. Such analyticalreactions are well known to one skilled in the art and need not befurther described here.

In another embodiment, an ammonium carbamate solution may be treatedwith a strong base in alcohol. For example, dimethylammoniumdimethylcarbamate is mixed with one molar equivalent of atetrabutylammonium hydroxide dissolved in ethanol. This yields atetrabutylammonium dimethylcarbamate solution after the neutralizationreaction, as well as dimethyl amine and water. An excess ofdimethylammonium dimethylcarbamate may also be used to ensure noresidual hydroxide is left in the initiator solution and/or to increasepot life and gel time. In another embodiment, a carbamate such asdimethylammonium dimethylcarbamate may be treated with a quaternaryammonium ethoxide solution in ethanol. This will yield a quaternaryammonium dimethylcarbamate solution in ethanol, dimethylamine but nowater is generated during the neutralization step.

In another embodiment, dimethylammonium dimethylcarbamate, is treatedwith an alcoholic solution of potassium t-butoxide to yield a solutionof potassium dimethylcarbamate, dimethylamine and t-butanol.

In another embodiment, a diethyl malonate solution in ethanol is treatedwith a quaternary ammonium ethoxide prior to adding dimethylammoniumdimethylcarbamate to yield a quaternary ammonium dimethylcarbamatesolution in ethanol mixed with diethyl malonate and dimethylamine. Inyet another embodiment, a quaternary ammonium hydroxide base, such asfor instance, tetrabutylammonium hydroxide is added to a solution ofdiethyl malonate in ethanol. Next, dimethylammonium dimethylcarbamate isadded to yield a tetrabutylammonium dimethylcarbamate solution mixedwith diethyl malonate, dimethylamine and water. In yet anotherembodiment, a strong alkoxide base like sodium ethoxide is added to asolution of diethyl malonate in ethanol. Next, a quaternary ammoniumchloride salt is added, for instance tributylmethylammonium chloride,and the solution is filtered to remove sodium chloride salt. Next, astoichiometric amount of dimethylammonium dimethylcarbamate is added toyield a solution of diethyl malonate, tributylmethylammonium carbamateand dimethylamine in ethanol. Malonate resin ingredient A may also beused in such reactions. In a certain embodiment, optionally in thepresence of an organic solvent, resin ingredient A is first treated witha quaternary ammonium base, preferably a quaternary ammonium hydroxidesolution, before adding an ammonium carbamate, potentially in excess, toyield a mixture of resin ingredient A, quaternary ammonium carbamate andamine.

In yet other embodiments, dialkyl ammonium dialkylcarbamates, ormonoalkyl ammonium monoalkylcarbamates or ammonium carbamate or mixturesthereof may also be used but those derived from smaller amines arepreferred. Ammonium carbamates are readily prepared by reacting carbondioxide with ammonia or amine. Mixtures of amines can also be used toprepare ammonium carbamate(s). Carbamate metal salt solutions can alsobe prepared as described in U.S. Pat. No. 5,808,013.

In certain embodiments, A^(n+) of formula 1 is a monovalent quaternaryammonium compound and the structure of this cation is shown in formula2. A large selection of such quaternary ammonium compounds iscommercially available from various manufacturers. In one embodiment,quaternary ammonium compounds are derived from tertiary amines which maybe quaternized with a methyl or benzyl group. In one embodiment, tetraalkyl ammonium compounds also can be used. R₃, R₄ and R₅ areindependently selected and are linear or branched alkyl chains havingfrom 1 to 22 carbon atoms. In some such embodiments, ammonium compoundswhere R₃, R₄ and R₅ are independently selected and range from 1 to 8. Insome other such embodiments, ammonium compounds can be identified withinthis group and is dependent upon performance and raw materials costs. Incertain embodiments, R₆ is a methyl or a benzyl group or an alkyl grouphaving from 1 to 22 carbon atoms or from 2 to 6 carbon atoms. Thequaternary ammonium compound is commercially available as a salt and theanion typically is chloride, bromide, methyl sulfate, or hydroxide.Quaternary ammonium compounds with methylcarbonate or ethylcarbonateanions are also available.

Examples of A^(n+) of formula 1 include dim ethyl diethylammonium,dimethyldipropylammonium, triethylmethylammonium,tripropylmethylammonium, tributylmethylammonium,tripentylmethylammonium, trihexylmethylammonium tetraethylammonium,tetrapropylammonium, tetrabutylammonium, tetrapentylammonium,tetrahexylammonium, benzyltrimethylammonium, benzyltriethylammonium,benzyltripropylammonium, benzyltributylammonium, benzyltripentyammonium,benzyltrihexylammonium or combinations thereof.

In another embodiment of the invention, polyamines, potentially incombination with monoamines, may also be utilized as raw material forcarbamate formation. In such embodiments, dormant carbamate initiatorsystems may also be derived from such carbamates when at least a part ofthe protonated ammonium cations in these ammonium carbamate salts arereplaced for quaternary ammonium cations, or other cationic species, orcationic polymers using synthetic approaches described above. Forinstance, piperazine is known to have a high capacity for carbon dioxidecapture and shows a high heat of absorption as well. Piperazine formsvarious carbamates, e.g. protonated piperazine carbamate, piperazinecarbamate and/or piperazine bicarbamate salts with mono or di protonatedpiperazine. The formation/decomposition equilibrium of carbamates istemperature dependent and varies depending on the amine employed as wellas solvent/environment. In another embodiment, carbamates may be derivedfrom pyrrolidine, 2-methylpyrrolidine, 3-methylpyrrolidine, piperidine,piperazine, methylethanolamine, diethanolamine, isopropanolamine,diisopropanolamine.

In yet another embodiment, carbamates may be derived from amines thathave a pKa greater than 7, or carbamates derived from amines that have apKa greater than 8, or carbamates derived from amines that have a pKagreater than 9, or carbamates that are derived from amines that have apKa greater than 10.

Formulation of Crosslinkable Composition

The crosslinkable composition useful as a coating can be formulated as aone component, a two component system or a three component system. In anembodiment of a two component system, initiator ingredient C is added toa mixture of ingredients A and B just prior to use. In an alternativeembodiment, ingredients A and C are mixed, and ingredient B is addedprior to use. In yet another embodiment, ingredient A is added to amixture of ingredients B and C prior to use. The dormant carbamateinitiator allows for an opportunity to formulate a three component paintsystem. In certain embodiments, pot life, working time and gel time canbe adjusted by selection of the carbamate structure, the amount used inthe crosslinkable composition, presence of additional ammonium carbamateand to a certain extent the amount of solvent and/or water. A gel timeof hours, and even days can be readily achieved, and gel times of weeksare possible. In such embodiment of a one component system, ingredientsA, B and C are mixed together, optionally with other ingredients toformulate a paint, which is then canned and stored until use. In certainembodiments, a one component system can be enhanced by means of usingexcess carbon dioxide gas over the crosslinkable composition as tofurther improve pot life and gel time. For instance, a paint compositionformulated according to the invention may have a protective atmosphereof carbon dioxide over the paint volume; and in yet another embodiment,a container containing the crosslinkable composition may even bepressurized with carbon dioxide. In another embodiment, a one componentsystem containing ingredients A, B and C are in a container filled tocapacity with essentially no space remaining for other solid, liquid orgaseous ingredients optionally containing ammonium carbamate. In yetanother embodiment, additional ammonium carbamate may further enhancestability in such one component coating formulations.

In another embodiment, the present invention provides for thecrosslinkable coating composition wherein ingredient A, ingredient B andthe carbamate initiator are contained in a container having two or morechambers, which are separated from one another. In one such embodiment,ingredient A and ingredient B are contained in separate chambers toinhibit any reaction. In another such embodiment, the carbamateinitiator is contained in the chamber having ingredient A, andoptionally containing CO₂ and/or ammonium carbamate. In another suchembodiment, the carbamate initiator is contained in the chamber havingingredient B, and optionally containing CO₂ and/or ammonium carbamate.

In another embodiment, the present invention provides for thecrosslinkable coating composition such that ingredient A and ingredientB are contained in the same chamber and the carbamate initiator iscontained in a separate chamber to inhibit any reaction and saidseparate chamber optionally containing CO₂ and/or ammonium carbamate.

In another embodiment, the present invention provides for thecrosslinkable coating composition wherein ingredient A and ingredient Band carbamate initiator are contained in a container having a singlechamber, wherein the container optionally contains CO₂ and/or ammoniumcarbamate.

Malonate esters are known to be susceptible to base hydrolysis,particularly when water is present. Water potentially can lead toundesirable destruction of initiator by means of formation of malonatesalt and it can degrade malonate oligomers or polymers, which in turncan lead to altered coatings performance. Transesterification reactionsalso can occur with malonate esters and alcohol solvent. These reactionspotentially can be limiting to the formulation of an acceptable workinglife, as a coating formulator seeks to increase pot life and gel timefor a crosslinkable composition formulated either as a one or twocomponent system. However, primary alcohols such as methanol and ethanolare much more active in transesterification reactions than secondaryalcohols such as isopropanol, while tertiary alcohols are generallyleast active. Furthermore, additional resistance towards hydrolysis andtransesterification can be obtained when malonate polyester resins arederived from malonic acid, or a dialkyl malonate such as diethylmalonate, and polyols bearing secondary alcohol groups; such as2,3-butanediol, 2,4-pentanediol and 2,5-hexanediol and the like. Thecombination of such polyester resins and non-primary alcohol solvents,such as isopropanol or isobutanol, is particularly useful in achievingdesirable resistance towards transesterification reactions. In a certainembodiment, resin ingredient A comprises malonate moieties that havebeen esterified with polyols bearing secondary alcohol groups and wheresecondary alcohol is present as solvent in the crosslinkable compositionof this invention. In yet another embodiment, tertiary alcohols are usedas solvent or solvents as used that do not participate intransesterification reactions. Other resins may also be formulated usingsuch stabilizing approaches towards resin breakdown and such approachesare well known to one skilled in the art and need not be furtherdescribed here.

In one embodiment, the crosslinkable composition of this inventioncomprising ingredients A, B and C may optionally contain an additionalingredient D, which once activated, can react with the Michael acceptor.In one such embodiment, ingredient D has one or more reactive protonsthat are more reactive, i.e. more acidic than those of ingredient A (thepKa of ingredient D is lower than that of ingredient A) yet not asreactive as ammonium carbamate with respect the pKa. In anotherembodiment, ingredient D may be more acidic than ammonium carbamate withrespect to pKa. In such embodiments, the reactive protons of ingredientD are present at a fraction based on the reactive protons of ingredientA where the fraction ranges from 0 to 0.5, or from 0 to 0.35, or between0 and 0.15.

Examples of ingredient D include; succinimide, isatine, ethosuximide,phthalimide, 4-nitro-2-methylimidazole, 5,5-dimethylhydantioin, phenol,1,2,4-triazole, ethylacetoacetate, 1,2,3-triazole, ethyl cyanoacetate,benzotriazole, acetylacetone, benzenesulfonamide, 1,3-cyclohexanedione,nitromethane, nitroethane, 2-nitropropane, diethyl malonate,1,2,3-triazole-4,5-dicarboxylic acid ethyl ester,1,2,4-triazole-3-carboxylic acid ethyl ester, 3-Amino-1,2,4-triazole,1H-1,2,3-triazole-5-carboxylic acid ethyl ester,1H-[1,2,3]triazole-4-carbaldehyde, morpholine, purines such as purine,adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uricacid and isoguanine; pyrimidines, such as thymine and cytosine; uracil,glycine, ethanimidamide, cysteamine, allantoin, N,N-dimethylglycine,allopurinol, N-methylpyrrolidine, benzeneboronic acid, salicylaldehyde,3-hydroxybenzaldehyde, 1-naphthol, methylphenidate and Vitamin E.

In certain embodiments, ingredient D can significantly affect theinitial cure speed and thus can generate longer open time.

In another embodiments, ingredient D may be incorporated into resiningredient A. In such an embodiments, substituted succinimides,including hydroxyl group containing succinimide derivatives,3-hydroxy-2,5-pyrrolidinedione and3-(hydroxymethyl)-2,5-pyrrolidinedione, or carboxylic acid groupcontaining succinimide derivative, 2,5-dioxo-3-pyrrolidinecarboxylicacid can undergo condensation reactions with either acid/ester groups orhydroxyl groups at the end of resin A polymer chain, where thesuccinimide moiety will be incorporated into the polymer backbone as endcap.

In yet another embodiment, maleimides can be copolymerized via radicalprocess with acetoacetoxyethyl methacrylate (AAEM) to a copolymer thatcontains both acetoacetate group and succinimide groups.

In certain embodiments, the crosslinkable coating composition of thisinvention can comprise one or more pigments, dyes, effect pigments,phosphorescent pigments, flakes and fillers. Metal flake effect pigmentsmay also be used in the crosslinkable coating composition of thisinvention and this is an advantage over UV curable nail gel coatings asthe UV cure process is hindered by such pigments and these metal flakesare therefore typically not used in such long lasting nail coatings.

The crosslinkable coating compositions of this invention may contain oneor more of FD&C or D&C dyes, pigments, lakes and combinations thereof.Lakes are colorants where one or more of the FD&C or D&C dyes areadsorbed on a substratum, such as alumina, blanc fixe, gloss white,clay, titanium dioxide, zinc oxide, talc, rosin, aluminum benzoate orcalcium carbonate. In certain embodiments, the D&C dye is independentlyselected from D&C Red No. 30, D&C Red No. 33, D&C Black No. 2, D&CYellow No. 5, D&C Green No. 5, Annatto, Caramel and combinationsthereof. In certain embodiments, the inorganic pigment is selected fromthe group consisting of red iron oxide; yellow iron oxide; titaniumdioxide; brown iron oxide; chromium oxide green; iron blue (ferricferrocyanide blue); ultramarine blue; ultramarine violet; ultramarinepink; black iron oxide; bismuth oxychloride; aluminum powder; manganeseviolet; mica; bronze powder; copper powder; guanine and combinationsthereof.

In certain embodiments, the crosslinkable coating composition of thisinvention can comprise other Michael addition reactive and non-reactiveresins or polymers, for instance to facilitate adhesion, and/or aid incoating removal. Such removal aids may be solvent-dissolvable compounds,resins, oligomers or polymers, which are dispersed in the polymerizedstructure and can be easily dissolved by a solvent to facilitate solventabsorption and migration during removal of the coating.

In certain other embodiments, the crosslinkable coating composition ofthis invention may optionally comprise resins, such as, but not limitedto nitrocellulose, polyvinylbutyral tosylamide formaldehyde and/ortosylamide epoxy resins. Such resins may act as film formers, adhesionpromoters, and aids to removal. These resins may also qualify assolvent-dissolvable resins. Nonreactive polymers may also be added tothe formulation, and compounds such as 1,3-butanediol may optionally beadded to alter properties such as gloss.

In some embodiments, the crosslinkable coating composition of thisinvention can comprise optional additives such as wetting agents,defoamers, rheological control agents, ultraviolet (UV) lightstabilizers, dispersing agents, flow and leveling agents, opticalbrighteners, gloss additives, radical inhibitors, radical initiators,adhesion promotors, plasticizers and combinations thereof.

Nail Coating Compositions

In some embodiments, the crosslinkable composition of this inventionformulated as a nail polish may be packaged in a single unit packagegood for one time use. Such single serve units contain enough coatingmaterial to decorate all finger and toe nails. A single use package maycontain a nail polish formulated as a one component system where allingredients are mixed in one chamber, optionally with extra ammoniumcarbamate and carbon dioxide to push back on the dormant carbamateinitiator or in one chamber filled to capacity with essentially no spaceremaining for other solid, liquid or gaseous ingredients. The singleunit package may contain more than one chambers when the nail polishsystem is formulated as a multi component system, e.g. two chambers whenthe nail polish is formulated as a two component system, or threechambers when ingredients A, B and C are all kept separate until use.Packages are known where a seal between chambers is broken to allow formaterials to be mixed in the merged chambers and a proper ratio ofcomponents is maintained by virtue of the design of the package.Flexible packages and more rigid containers such as bottles that havemore than one chamber where contents can be mixed upon demand are knownand are readily available. Single unit packages may also include a brushfor application. In another approach deviating from a single useconcept, material may be dispensed from a single chamber (flexible)package that can be resealed. Multi chamber package that utilizeplungers are also known and proper mixing of components can be insuredby use of a mixing nozzle for instance. Material may be dispensedmultiple times provided the time between uses does not exceed theworking life of the nail polish in a mixing chamber or if the workinglife is to be exceeded, the mixing nozzle is removed and the packagecapped and stored until future use when a new mixing nozzle will beused. Many packaging solutions are available from packaging providersand these are well known to one skilled in the art.

In an embodiment, the crosslinkable coating composition of thisinvention is particularly useful to decorate finger and toe nails, andcan be applied as a three coat nail polish system, with a base coatapplied directly on top of the base nail surface, followed by a colorcoat and finished with a glossy top coat. In another embodiment, thenail polish system is formulated as a two coat system, where a colorcoat is applied directly on the bare nail surface, and finished with aglossy top coat, but in yet another embodiment, and base coat is appliedto the nail surface to provide adhesion for a glossy color coat. Anotherembodiment to decorate nails is where the crosslinkable coatingcomposition of this invention is used as a single coat system, which hasgood adhesion to the nail surface, color and gloss all in a one coatsystem. It is understood that multiple coats can be applied over a samecoat for any of these one, two or three coat systems.

The following examples further describe and demonstrate illustrativeembodiments within the scope of the present invention. The examples aregiven solely for illustration and are not to be construed as limitationsof this invention as many variations are possible without departing fromthe spirit and scope thereof.

Example 1

Synthesis of Carbamate Initiator by Means of Ion Exchange.

A glass column fitted with a frit at the bottom was charged with 55 g ofAmberlite IR 120 Na cation exchange resin, which was then swollen withdistilled water. The resin was then washed 3 times with 200 ml water,and charged with 10 wt. % of tributylmethylammonium chloride (TBMA Cl)in water solution. To maximize the ion exchange, the charging processwas repeated three times. The ion exchange efficiency was followedgravimetrically. After charging the resin with tributylmethylammonium(TBMA) cations and washing free of excess TBMA Cl, the resin was madewater free by washing it with anhydrous ethanol. Washing was continueduntil the water content of the wash ethanol fell below 0.07 wt. % asdetermined by coulometric Karl-Fischer titration. Next, a 10 wt. %solution of dimethylammonium dimethylcarbamate (DMA DMC) in anhydrousethanol was passed through the charged resin. Not more than 35% of theresin ion exchange capacity was utilized to ensure a complete conversionof DMA DMC. The tributylmethylammonium dimethylcarbamate (TBMA DMC)initiator was characterized by nuclear magnetic resonance (NMR) analysisand Fourier transform infrared spectroscopy (FTIR) and was titrated withacid and base to assess concentration. In a similar manner, TBMA DMCcarbamate initiators were prepared in 1-propanol and 2-propanol.

Example 2

Synthesis of Carbamate Initiator by Neutralization of MalonateCarbanion.

To a 250 ml single neck round-bottom flask was charged 5.0 g of diethylmalonate (DEM) and 28.2 g of a 1.0 M solution of potassium t-butoxide intetrahydrofuran (THF). A white precipitate was immediately observed. Atthe end of addition, 50.0 g of anhydrous isopropanol was added to thereaction mixture under constant stirring to obtain a homogeneous whitesuspension. Then 7.36 g of dry TBMA Cl was mixed into the flask,stirring was continued for another 10-15 minutes before 4.19 g of DMADMC was added. The reaction mixture was continuously stirred at roomtemperature for one hour, and white suspension was removed by filtrationand a clear carbamate initiator solution was obtained free of water.

Example 3

General Synthesis of Carbamate Initiator by Neutralization of QuaternaryAmmonium Hydroxide.

Most of the methanol solvent from a 40 g tetrabutylammonium hydroxide(TBA OH) solution in methanol (1 M) was removed with a rotaryevaporator. The material was not allowed to become completely drywithout solvent as dry quaternary ammonium hydroxide base wassusceptible to decomposition. Next, 40 grams of ethanol was added andmost of the solvent was again removed. This procedure was repeated atleast two more times until the methanol effectively has been replaced asdetermined by NMR. The solution strength was determined by titration(typically 1.7 mmol base/g solution). Solvent exchange was also carriedout to prepare TBA OH solutions in methanol (typical concentration 1.2mmol/g solution), 1-propanol (typical concentration of 1.1 mmol base/gsolution) and TBA OH in 2-propanol (typical concentration of 1.3 mmolbase/g solution). Next, about 25 g of TBA OH in ethanol was mixed withDMA DMC in a 1.0:1.1 molar ratio respectively at room temperature andstirred for 1 hour using a magnetic stirrer. The TBA DMC solution inethanol was light yellow and was characterized by means of acid and basetitrations (potentiometric and with indicator), back titrations and NMR.In a similar manner, TBA DMC solutions were prepared in methanol,1-propanol and 2-propanol. These initiators were designated as initiatorII and the alkanol name was used to indicate the alcohol solvent. TBADMC solutions in the four alcohols were also prepared using a 1.0:1.5molar ratio of TBA OH and DMA DMC respectively, and these initiatorswere designated as initiator III and again, the alkanol name was used toindicate the alcohol solvent.

Example 4

General Synthesis of Carbamate Initiator by Neutralization of QuaternaryAmmonium Ethoxide.

Tributylmethylammonium chloride (TBMA Cl), 10 g, was dissolved inethanol and mixed in 1:1 molar ratio with a 20 wt. % solution ofpotassium ethoxide in ethanol. The mixture was allowed to stir for 30min, and the precipitate was then removed by centrifugation. Theconcentration of TBMA ethoxide solution thus obtained was determinedpotentiometrically by means of titration with 0.1 N HCl solution. Thetypical concentration of TBMA ethoxide was about 1.1 mmol/g. Next, about25 g of TBMA ethoxide in ethanol was mixed with DMA DMC in a 1.0:1.1molar ratio respectively at room temperature and stirred for 1 hourusing a magnetic stirrer. The TBMA DMC solution in ethanol was lightyellow in color and is characterized by means of acid and basetitrations (potentiometric and with indicator) and NMR.

Example 5

General Synthesis of Carbonate Catalyst.

The methanol solvent of TBA OH solution (1 M) in methanol was replacedwith ethanol as described in example 3. Next, a precise amount of theTBA OH in solution was mixed with diethyl carbonate (DEtC) in a 1:5molar ratio respectively and stirred for 1 hour at room temperatureusing magnetic stirrer. The final clear catalyst solution was analyzedby means of titration and NMR. In a similar manner, clear solutions wereobtained in 1-propanol and 2-propanol. A solution made using the TBA OHbase in methanol resulted in white precipitate which was removed bycentrifuge followed by filtration using 0.45μ syringe filter. In asimilar approach, catalyst solutions were prepared in various alcoholsusing TBA OH and dimethylcarbonate (DMeC). Transesterification reactionproducts were observed in the NMR for all cases where the carbonatealkyl group was different from the solvent, e.g. ethanol formation wasobserved when DEtC was added to TBA OH in isopropanol and isopropylgroups associated with carbonates were also observed.

Example 6

Malonate Resin (I) Synthesis.

A 3 liter reactor was charged with 500 g of diethylene glycol (DEG) and1509 g of diethyl malonate (DEM). The reactor was equipped with aDean-Stark apparatus, mechanical stirrer, nitrogen flow and heatingequipment. The mixture was heated to about 180° C. with stirring undernitrogen atmosphere. During a four hour reaction time, about 450 ml ofethanol was collected. Next, the temperature was reduced to 115° C. anda vacuum distillation was initiated to remove about 246 g of DEM. Thefinal product was a lightly yellow colored liquid with less than 0.15wt. % of residual DEM as determined by gas chromatography (GC). Gelpermeation chromatography (GPC) analysis showed three peak molecularweight of 900, 600 and 400 g/mol and the malonate methylene equivalentmolecular weight of 156 g/mol.

Example 7

Malonate Resin (II) Synthesis.

A reactor was charged with 600 g of polyethylene glycol (PEG 300) and640 g of DEM and the reaction synthesis procedure was followed fromexample 6. The reaction yielded a total of about 170 ml of ethanol and118 g of DEM was removed by distillation. Analysis showed that the lightyellow product contains less than 0.1 wt. % of DEM, Mn-1000 g/mol andmalonate methylene equivalent molecular weight of 292 g/mol.

Example 8

Malonate Resin (III) Synthesis.

A reactor was charged with 30 g of trimethylolpropane (TMP), 107 g ofDEM and 17.7 g of tert-butyl acetoacetate (tBAA) and the reactionsynthesis procedure was followed from example 6. The reaction resultedin about 25 g of alcohol and 36 g of material was removed bydistillation. The light yellow product contains <0.1% of DEM, Mn-2100g/mol and malonate methylene equivalent molecular weight of 142 g/mol.

Example 9

Malonate Resin (IV) Synthesis.

A reactor was charged with 40 g of glycerol (Gly), 68.71 g of DEM and69.5 g of tBAA were charged to the reactor and the reaction synthesisprocedure was followed from example 6. The reaction resulted in 45 g ofalcohol collection and 3 g of material was removed by distillation. Thelight yellow product contained <0.1% of DEM, Mn-1400 g/mol and malonatemethylene equivalent molecular weight of 145 g/mol.

Example 10

Acetoacetate Modified Polyol.

A reactor (500 ml capacity) was charged with 175 g of STEPANPOL®PC-2011-225 (a commercial polyol resin with hydroxyl value of 225 mg ofKOH/g of sample), and 133 g of tertiary butyl acetoacetate. The reactorwas equipped with Dean-Stark apparatus, mechanical stirrer, nitrogenflow and heating equipment. The mixture was heated to about 180° C. withstirring under nitrogen atmosphere. In four hours, 55 ml of alcohol werecollected and no further distillate was obtained. The reactiontemperature was lowered to 115° C. and a vacuum distillation resulted incollection of a total 6 g of tertiary butyl acetoacetate. The finalproduct was light yellow colored with methylene equivalent molecularweight of 306 g/mol (calculated based on the theoretical mole ratio andthe tertiary butanol and tertiary butyl acetoacetate collected amount).

Example 11

Malonate Resin (V) Synthesis.

A 500 ml reactor was charged with 66.25 g of DEG, 125.0 g of DEM, 40.65g of 1-octanol and 4-5 drops of titanium (IV) butoxide. The reactor wasequipped with a Dean-Stark apparatus, mechanical stirrer, nitrogen flowand heating equipment. The mixture was heated to about 180° C. withstirring under nitrogen atmosphere. During a four hour reaction time,about 80 ml of ethanol were collected. The final product was a slightlyyellow liquid with 0.75 wt. % of residual DEM and 0.95% wt. % ofresidual 1-octanol as determined by GC. GPC analysis showed Mw/Mn (PDI)of 1944/1550 (1.25) in g/mol and a malonate methylene equivalentmolecular weight of 205.0 g/mol.

Example 12

Malonate Resin (VI) Synthesis.

A 500 ml reactor was charged with 92 g of 1,6-hexanediol (HD), 150 g ofDEM, 52 g of diethylene glycol monoethylether (DEGMEE) and 4-5 drops oftitanium (IV) butoxide. The reactor was equipped with a Dean-Starkapparatus, mechanical stirrer, nitrogen flow and heating equipment. Themixture was heated to about 180° C. with stirring under nitrogenatmosphere. During a four hour reaction time, about 110 ml of ethanolwere collected. The final product was a lightly yellow colored liquidwith less than 0.15 wt. % of residual DEM as determined by GC. GPCanalysis showed Mw/Mn (PDI) 2205/1141 (1.93) in g/mol and the malonatemethylene equivalent molecular weight of 216 g/mol.

Example 13

Substituted Malonate Resin (VII) Synthesis.

A reactor was charged with 130 g HD, 250 g of diethyl methylmalonate(DEMM), also known as propanedioic acid, 2-methyl-, 1,3-diethyl ester,74 g of DEGMEE and 4-5 drops of titanium (IV) butoxide. The reactionsynthesis procedure was followed from example 12. The reaction yielded atotal of about 146 ml of ethanol. Analysis shows that the light yellowproduct contained less than 0.1 wt. % of DEMM, Mw/Mm (PDI) 2111/1117(1.89) in g/mol and malonate methylene equivalent molecular weight of230 g/mol.

Example 14

Substituted Malonate Resin (VIII) Synthesis.

A reactor was charged with 121 g HD, 240 g of diethyl ethylmalonate(DEEM), 68 g of DEGMEE and 4-5 drops of titanium(IV) butoxide. Thereaction synthesis procedure was followed from example 12. The reactionyielded a total of about 144 ml of ethanol. The light yellow productcontained <0.1% of DEEM, Mw/Mn (PDI) 2894/1450 (2.0) in g/mol andmalonate methylene equivalent molecular weight of 244 g/mol.

Example 15

Malonate Resin (IX) Synthesis.

A 500 ml reactor was charged with 118.76 g of 1,3-propanediol (PD),250.0 g of DEM and 4-5 drops of titanium (IV) butoxide. The reactor wasequipped with a Dean-Stark apparatus, mechanical stirrer, nitrogen flowand heating equipment. The mixture was heated to about 180° C. withstirring under nitrogen atmosphere. During a four hour reaction time,about 160 ml of ethanol were collected. The final product was acolorless liquid. GPC analysis showed Mw/Mn (PDI) of 4459/2226 (2.0) ingram/mole and a malonate methylene equivalent molecular weight of 144.12g/mol.

Example 16

Malonate Resin (X) Synthesis.

A 500 ml reactor was charged with 206.6 g of HD, 280.0 g of DEM and 4-5drops of titanium (IV) butoxide. The reactor is equipped with aDean-Stark apparatus, mechanical stirrer, nitrogen flow and heatingequipment. The mixture was heated to about 180° C. with stirring undernitrogen atmosphere. During a four hour reaction time, about 180 ml ofethanol were collected. The final product was a lightly yellow coloredliquid with less than 0.04 wt. % of residual DEM and less than 1.34 wt %of residual HD as determined by GC. GPC analysis showed Mw/Mn (PDI) of8399/3366 (2.5) in gram/mole and a malonate methylene equivalentmolecular weight of 186.21 g/mol.

Example 17

Malonate Resin (XI) Synthesis.

A 500 ml reactor was charged with 91.85 g of HD, 155.6 g of DEM, 52.14 gof DEGMEE and 4-5 drops of titanium (IV) butoxide. The reactor wasequipped with a Dean-Stark apparatus, mechanical stirrer, nitrogen flowand heating equipment. The mixture was heated to about 180° C. withstirring under nitrogen atmosphere. During a four hour reaction time,about 100 ml of ethanol were collected. The final product was a lightlyyellow colored liquid with less than 0.05 wt. % of residual DEM asdetermined by GC. GPC analysis showed Mw/Mn (PDI) of 2320/1616 (1.44) ingram/mole and a malonate methylene equivalent molecular weight of 216.25g/mol.

Example 18

Malonate Resin (XII) Synthesis.

A 500 ml reactor was charged with 132.81 g of HD, 150.0 g of DEM, 59.26g of tBAA and 4-5 drops of titanium (IV) butoxide. The reactor wasequipped with a Dean-Stark apparatus, mechanical stirrer, nitrogen flowand heating equipment. The mixture was heated to about 180° C. withstirring under nitrogen atmosphere. During a six hour reaction time,about 120 ml of ethanol/t-butanol mixture were collected. The finalproduct was a lightly yellow colored liquid with less than 0.40 wt. % ofresidual DEM and less than 1.0% wt. % of residual HD as determined byGC, no residual tBAA was detected. GPC analysis showed Mw/Mn (PDI) of2550/1242 (2.05) in gram/mole and a malonate methylene equivalentmolecular weight of 181.93 g/mol.

Example 19

Diurethane Diacrylate (DUDA) Michael Acceptor Crosslinker Synthesis.

A 500 ml capacity reactor was charged with 85 g of 2-hydroxyethylacrylate (HEA), a few drops of K-Kat 348 catalyst and 60 mg ofphenothiazine inhibitor. The reactor was equipped with a Dean-Starkapparatus, mechanical stirrer, nitrogen flow and heating equipment. Themixture was heated to about 50° C. with stirring under nitrogenatmosphere and 81 g of trimethylhexamethylene diisocyanate (TMDI) wasadded in a dropwise manner. After the addition was completed, thereaction was continued for another hour and excess isocyanate wasquenched using ethanol. Residual ethanol was removed under vacuum and atranslucent viscous product was collected as bis(2-hydroxyethylacrylate) trimethylhexyl dicarbamate.

Example 20

Malonate Resin (XIII) Synthesis.

A 500 ml reactor was charged with 149.8 g of PEG 300, 100 g of DEM, 32.5g of 1-octanol and 4-5 drops of titanium (IV) butoxide. The reactor wasequipped with a Dean-Stark apparatus, mechanical stirrer, nitrogen flowand heating equipment. The mixture was heated to about 180° C. withstirring under nitrogen atmosphere. During an eight hour reaction time,about 70 ml of ethanol were collected. The final product was a lightlyyellow colored liquid with less than 0.15 wt. % of residual DEM asdetermined by GC. GPC analysis showed Mw/Mn (PDI) of 4191/2818 (1.49) ingram/mole and a malonate methylene equivalent molecular weight of 360g/mol.

Coating Testing

Tack free time was evaluated by lightly pressing a gloved index fingerperiodically onto the coating. The time when visible marks in the filmare no longer left by the pressed finger, is then recorded as the tackfree time.

Gel time is taken as the amount of time it takes for a mixed, reactiveresin system to gel or become so highly viscous that it has lostfluidity. Typically, the various ingredients are charged into a 4 mlvial and closed with headspace volume as constant as possible to allowfor comparison and the sample is kept at room temperature and tilted atregular time intervals to determine whether the material still flows. Ifno flow is observed during tilting, the vial is held upside down and ifno further flow occurs the material is gelled.

Gloss was measured using a handheld Micro-Tri-Gloss meter from BYKInstruments. Measurements were taken at 60 degrees in three differentlocations on the film and the average is reported.

Pencil Hardness testing was performed according to the ISO 15184 testmethod at ambient laboratory conditions. The pencil hardness ratingscale is as follows: [Soft]9B-8B-7B-6B-5B-4B-3B-2B-B-HB-F-H-2H-3H-4H-5H-6H-7H-8H-9H [Hard].

Acetone removal was determined by placing a cotton ball in the center ofthe nail polish coating. Acetone was added to the cotton ball until theliquid layer barely showed at the edge of the cotton ball. Afterstarting the test, the cotton ball was briefly lifted to examine thecoating integrity below the cotton ball. In order to adjust for theacetone evaporation throughout the test time period, additional acetonewas added to the cotton ball to maintain that light liquid layer at theedge of the cotton ball. The time at which the surface integrity becamedisrupted was determined as the test end point.

Fineness of Grind was evaluated with a Hegman Gauge according to theASTM D1210 test method.

Film elasticity and resistance to cracking, elongation and/or detachmentfrom metal test panels was tested with a conical Mandrel bend tester.Test panels were prepared by casting a 3 mil film on aluminum substratesand the films are allowed to cure overnight before testing. Panelsfolded around the cone were visually examined for the cracks of thefilm. The point at which the cracking stops was marked and the distancefrom the farthest end of the crack to the small end of the mandrel wasmeasured and results were expressed on a 0 to 100% scale, with 100%showing no cracks or defects.

Both direct and reverse impact were tested with an impact tester, wherereverse impact is considered more severe a test than direct impact. Thetester consists of a solid base with a guide tube support. The guidetube has a slot to direct a weight that slides inside the guide tube,and graduations are marked along the slot to facilitate readings. Testpanels were first prepared by casting a 3 mil film on aluminumsubstrates, and films were allowed cure overnight before testing. Panelsare placed under the punch and the height of the impacter was adjusteduntil the reading (maximum height) is determined at which film doesn'tfail. The result is expressed as percent and calculated by the dividingthe maximum height/160.

To test for water blush, 3 mil films were cast on aluminum substratesand cured overnight. A drop of water is applied to the film to yield aspot of about 1-1.5 centimeter in diameter, which is then covered with abeaker and checked after an hour. White marks or swollen films wasconsidered failure.

Brushability time was determined as the length of time between theaddition of initiator up to the point when the mixture viscosityincreased so much that it became not possible to apply a uniformaesthetically pleasing layer of nail polish using a typical nail polishbottle brush applicator

Inventive Example 1

The TBMA DMC solution in ethanol prepared under example 1 was tested asdormant carbamate initiator. In a vial, 1.0 g of the malonate resinprepared under example 6 was mixed with 1.5 g of di-trimethylolpropanetetraacrylate (DTMPTA) and then 1.148 g of the TBMA DMC initiatorsolution in ethanol was added. The complete formulation was mixed welland then a test film was applied on a glass substrate to test curingbehavior. The coating film became tack-free within 5 minutes and the geltime of the material in the vial was longer than 24 hours. The carbamatewas a dormant initiator.

Inventive Example 2

A mixture was prepared in a vial combining 1.0 g of the malonate resinprepared under example 6 and 1.27 g of trimethylolpropane triacrylate(TMPTA). Next, 1.3 g of the TBMA DMC carbamate solution prepared inexample 2 was added to the vial and the liquid was mixed well. A filmwas then applied onto a glass slide and the coating became tack freewithin 5 minutes. No gelation of the material in the vial was observedafter three weeks of aging. Another film was prepared of this agedmixture and again the coating cured within 5 minutes. Hence, thecarbamate was an effective dormant initiator.

Inventive Example 3

Three TBA DMC solutions in anhydrous ethanol are compared and tested asdormant initiator. Initiator I was a TBA DMC solution in anhydrousethanol prepared per the cation exchange procedure as set forth inexample 1. Initiator II was prepared in example 3 from TBA OH and DMADMC in a 1.0:1.1 molar ratio, and initiator III was prepared using a1.0:1.5 molar ratio. A resin mixture was formulated from the malonateresin prepared under example 6 and TMPTA. The molar ratio for malonatemethylene CH₂ to TMPTA to initiator was 3:2:0.2 respectively. Thepercent water for the carbamate initiator obtained by means ofneutralization was calculated from reaction stoichiometry and is basedas percentage of the total crosslinkable formulation. Anhydrous ethanolwas added as necessary to arrive at a comparable percent solventcontent. The ethanol solvent content is also based on total weight ofthe crosslinkable formulation. The tack free time of a film applied on aglass substrate was assessed as well as gel time. Data provided in table1 show that all three carbamate solutions are active as a dormantcarbamate initiator and they become effective once the initiatoractivates by means of film formation.

TABLE 1 Carbamate initiator Wt. % Water Wt. % Ethanol Tack free time Geltime I 0.0 32.7 140 sec >72 h II 0.2 31.8 140 sec >72 h III 0.2 31.2 120sec >72 h

Inventive Example 4

Initiator II was prepared in example 3 from TBA OH in ethanol,1-propanol or 2-propanol with TBA OH to DMA DMC in a 1.0:1.1 molarratio. Initiator III was prepared also in ethanol, 1-propanol or2-propanol and the TBA OH to DMA DMC molar ratio employed was 1.0:1.5respectively. The initiators were used either without addition ofadditional water, or water was added to these initiator solutions totarget about 1.2 wt. % water content based as percentage of the finalcrosslinkable formulation. At 1.2 wt. % water content, there is about4.5 moles of water per mole of initiator present. Similarly, a 10-15 wt.% alcohol content was targeted based on the final crosslinkableformulation. A resin mixture was formulated from the malonate resinprepared under example 6 and TMPTA. The molar ratio for malonatemethylene CH₂ to TMPTA to initiator was chosen at 3:2:0.2 respectively.Films were applied on a glass substrate to test for tack free time.Results shown in table 2 indicate that both carbamate initiators aredormant while the formulation remains in the vial, while good activationoccurs once a film is applied. The coating formulation in ethanol showsa longer gel time than 1-propanol and 2-propanol for initiator II, butthis can be improved by adding a little additional water and solvent.Addition of additional DMA DMC to the carbamate initiator system alsoimproves gel time when initiator II and III are compared but this doesnot seem to significantly impact tack free time.

TABLE 2 Carbamate Wt. % Wt. % Tack free initiator Solvent Water Solventtime Gel time II Ethanol 0.3 8.3  90 sec >16 h II 1-propanol 0.3 8.3  90sec  6-8 h II 2-propanol 0.3 8.3 <90 sec  6-8 h II Ethanol 1.2 12.9 140sec >16 h II 1-propanol 1.2 12.9 140 sec >16 h II 2-propanol 1.2 12.9140 sec >16 h III Ethanol 0.3 9.1  90 sec >24 h III 1-propanol 0.3 9.1 90 sec >24 h III 2-propanol 0.3 9.1 <90 sec >24 h III Ethanol 1.2 12.9120 sec >24 h III 1-propanol 1.2 12.9 120 sec >24 h III 2-propanol 1.212.9 130 sec >24 h

Comparative Example 1 (Versus Inventive Example 3 and 4)

Diethyl carbonate derived catalysts were prepared in ethanol, 1-propanoland 2-propanol as per example 5. Water content was fixed at either 0 wt.%, or water was added to the catalyst solutions to target about 1.2 wt.% water content based as percentage of the final crosslinkableformulation. At 1.2 wt. % water content, there is about 4.5 moles ofwater per mole of blocked base catalyst present. The catalyst solutionswere tested as blocked catalyst in a resin mixture formulated from themalonate resin prepared under example 6 and TMPTA using a molar ratiofor malonate methylene CH₂ to TMPTA to catalyst of 3:2:0.2 respectively,which is similar to inventive examples 3 and 4. Results shown in table 3indicate that the carbonate solutions are not active as a blockedcatalyst in ethanol, 1-propanol or 2-propanol in the absence of water,and even addition of water up to 1 wt. % of the total formulation doesnot lead to effective blocking of the carbonate base catalyst in thesesolvents. No tack free time could be measured because theresin—carbonate catalyst mixture polymerized immediately and an instantgel was formed.

TABLE 3 Carbonate Wt. % Wt. % Tack free catalyst Solvent Water Solventtime Gel time DEtC Ethanol 0.0 14.4 Instant gel <30 sec DEtC 1-propanol0.0 14.4 Instant gel <30 sec DEtC 2-propanol 0.0 14.4 Instant gel <30sec DEtC Ethanol 1.2 14.3 Instant gel <30 sec DEtC 1-propanol 1.2 14.3Instant gel <30 sec DEtC 2-propanol 1.2 14.3 Instant gel <30 sec

Comparative Example 2 (Versus Inventive Example 3 and 4)

The experiment of comparative example 1 was repeated except thatdimethyl carbonate catalyst solutions were used as prepared per example5. Results presented in table 4 show that the blocking is not effectivein these solvents when water is absent, and even addition of water up toabout 1 wt. % of the total formulation does not produce an effectiveblocking effect.

TABLE 4 Carbonate Wt. % Wt. % Tack free catalyst Solvent Water Solventtime Gel time DMeC Ethanol 0.0 12.9 Instant gel <30 sec DMeC 1-propanol0.0 12.9 Instant gel <30 sec DMeC 2-propanol 0.0 12.9 Instant gel <30sec DMeC Ethanol 1.2 12.9 Instant gel <30 sec DMeC 1-propanol 1.2 12.9Instant gel <30 sec DMeC 2-propanol 1.2 12.9 Instant gel   45 sec

Inventive Example 5

The experiment of inventive example 4 is repeated except methanol isused as solvent for initiator II and III and results are shown in table5. Both carbamate solutions are effective and carbamate is active as adormant initiator that activates once the coating formulations isapplied as a film.

TABLE 5 Carbamate Wt. % Wt. % Tack free initiator Solvent Water Methanoltime Gel time II Methanol 0.3 8.3 <90 sec   4 days III Methanol 0.3 9.1<90 sec >6 days

Comparative Example 3 (Versus Inventive Example 5)

A similar experiment is carried out as comparative examples 1 and 2 forDEtC and DMeC respectively, except methanol is used as the solvent andresults are shown in table 6.

TABLE 6 Carbonate Wt. % Wt. % Tack free catalyst Solvent Water Methanoltime Gel time DEtC Methanol 0.0 14.3 <90 sec 16 h DEtC Methanol 1.2 14.3<90 sec 6 days DMeC Methanol 0.0 13.0 <90 sec 16 h DMeC Methanol 1.212.9 <120 sec  >6 days

Inventive Example 6

About 1 ml of the initiators prepared in example 1 and example 3 (1:1.1ratio of TBMA OH to DMA DMC) with as-is concentration is each added to a2 ml clear vial. DMA DMC is also added to a vial for comparison. Thecarbamate solutions obtained via ion exchange are essentially free ofwater, while the carbamate solutions obtained via neutralization as perexample 3 contain an equal molar amount of water per amount ofinitiator. Next, 2 drops of phenolphthalein indicator is added to thesolution and mixed well. After mixing, the color is observed and a pinkcolor means the solutions is basic, while a colorless solution means nobase is present. The results are shown in Table 7. As expected, the TBMAOH solution has a pink color and is basic, but the carbamate solutionsare all colorless. Hence, the dormant carbamate initiator solutions arenot basic.

TABLE 7 Solution Materials Solvent color Comment DMA DMC — Colorless —TBMA OH Methanol Pink Active base TBMA OH + DMA DMC Methanol ColorlessDormant initiator TBMA OH + DMA DMC Ethanol Colorless Dormant initiatorTBMA OH + DMA DMC 1-propanol Colorless Dormant initiator TBMA OH + DMADMC 2-propanol Colorless Dormant initiator Ion exchanged TBMA DMCEthanol Colorless Dormant initiator Ion exchanged TBMA DMC 1-propanolColorless Dormant initiator Ion exchanged TBMA DMC 2-propanol ColorlessDormant initiator

Comparative Example 4 (Versus Inventive Example 6)

About 1 ml of the catalysts prepared in example 4 using TBMA OH and DEtCwith as-is concentration is each added to a 2 ml clear vial. Next, 2drops of phenolphthalein indicator is added to the solution and mixedwell. After mixing the final color change is observed as either pink orcolorless and results are tabulated in table 8. A pink colored solutionmeans the solution is basic and a colorless solutions means that thebase is blocked from activity. Only the base in methanol is blocked bythe carbonate but the base was not blocked by the carbonate in the otheralcohols and remained active as base.

TABLE 8 Materials Solvent Solution color Comment TBMA OH Methanol PinkActive base TBMA OH + DEtC Methanol Colorless Blocked catalyst TBMA OH +DEtC Ethanol Pink Active base TBMA OH + DEtC 1-propanol Pink Active baseTBMA OH + DEtC 2-propanol Pink Active base

Inventive Example 7

The dormant carbamate initiator was employed in a crosslinkable coatingcomposition as to formulate a nail polish system. The system utilizedthree coatings; a basecoat/primer, a color coat, and a topcoat to allowfor comparison against commercial UV nail gel and conventional (solventborne) nail polish systems, which also employ a three coat approach. Twonail polish systems (inventive example 7.1 and 7.2) were formulatedbased on the inventive crosslinkable composition.

Carbamate Initiator Synthesis:

Most of the methanol solvent from a 40 g tetrabutylammonium hydroxide(TBA OH) solution in methanol (1 M) was removed with a rotary evaporatorin about 30 minutes at room temperature. Next, 40 grams of ethanol(EtOH) was added and most of the solvent was again removed in a similarmanner. This procedure is repeated at least two more times until themethanol effectively has been replaced. The complete removal of methanolwas confirmed by ¹H NMR analysis. Next, 25 g of the TBAOH in EtOH (1.34mmol base/g solution) solution was mixed with 6.4 g DMA DMC at roomtemperature and stirred for 1 hour using magnetic stirrer. The finallight yellow solution had an initiator concentration of 1.38 mmol/gsample.

Base coat formulations: two different base coats were formulated.

Base coat A; formula ingredients: 4.55 wt. % of malonate resin (I) ofexample 6; 40.91 wt. % of malonate resin (II) of example 7; 19.91 wt. %of DTMPTA; 9.10 wt. % of butyl acetate (BA); 9.10% of ethyl acetate(EA); 1.83 wt. % of an alkyl ethoxylate wetting agent; and 14.60 wt. %of carbamate initiator. All the ingredients except the initiator wereweighed into a 20 ml vial. The vial was capped and the mixture shakenuntil visually homogenous. The dormant carbamate initiator was thenweighed into the mixture. The final mixture was capped and shaken for 30seconds, and then applied using a 3 mil Bird type film applicator on avitronail panel substrate.

Base coat B; formula ingredients: 7.28 wt. % of malonate resin (III) ofexample 8; 40.95 wt. % of malonate resin (II) of example 7; 19.93 wt. %of DTMPTA; 6.37 wt. % of BA; 9.10% of EA; 1.82 wt. % of an alkylethoxylate wetting agent; and 14.56 wt. % of carbamate initiator. Allthe ingredients except the initiator were weighed into a 20 ml vial. Thevial was capped and the mixture shaken until visually homogenous. Thedormant carbamate initiator was then weighed into the mixture. The finalmixture was capped and shaken for 30 seconds, and then applied using a 3mil Bird type film applicator on a vitronail panel substrate.

Color coat formulation: only one color coat A was formulated.

A Colorant Pigment Dispersion was prepared first. Formula ingredients:62.65 wt. % of malonate resin (I) of example 6; 37.35 wt. % of ChemoursTS-6200 white pigment. The resin was added to the stainless steel mixingvessel. Mixing of the resin was begun using a high speed dispersionmixer at 1.5 mm/s using a 50 mm mixing blade. The TS-6200 pigment waspoured at a medium rate into the mixing resin. After all of the TS-6200had been added, the mixing speed was increased to 7.85 m/s and heldconstant for 10 min. At the end of mixing, the mixture was poured into astorage jar and sealed.

Color coat A was formulated as follows: formula ingredients: 25.00 wt. %of the Colorant Pigment Dispersion; 9.15 wt. % of malonate resin (IV) ofexample 9; 6.10 wt. % malonate resin (II) of example 7; 35.37 wt. % ofDTMPTA; 12.20 wt. % of BA; 2.43 wt. % of an alkyl ethoxylate wettingagent; and 9.75 wt. % of carbamate initiator. All the ingredients exceptthe initiator were weighed into a 20 ml vial. The vial was capped andthe mixture shaken until visually homogenous. The dormant carbamateinitiator was then weighed into the mixture. The final mixture wascapped and shaken for 30 seconds, and then applied over the dried basecoat using a 3 mil Bird type film applicator.

Top coat formulations: two different top coats were formulated.

Top coat A; formula ingredients: 18.12 wt. % of malonate resin (I) ofexample 6; 10.87 wt. % of malonate resin (IV) of example 9; 7.25 wt. %of malonate resin (II) of example 7; 42.03 wt. % of DTMPTA; 7.25 wt. %of BA; 1.45 wt. % of 1,3-butanediol (BD); 1.44 wt. % of an alkylethoxylate wetting agent; and 11.59 wt. % of carbamate initiator. Allthe ingredients except the initiator were weighed into a 20 ml vial. Thevial was capped and the mixture shaken until visually homogenous. Thedormant carbamate initiator was then weighed into the mixture. The finalmixture was capped and shaken for 30 seconds, and then applied over thedried color coat using a 3 mil Bird type film applicator.

Top coat B; formula ingredients: 28.82 wt. % of malonate resin (III) ofexample 8; 10.37 wt. % of malonate resin (IV) of example 9; 6.91 wt. %of malonate resin (II) of example 7; 40.08 wt. % of DTMPTA; 1.38 wt. %of BD; 1.38 wt. % of an alkyl ethoxylate wetting agent; and 11.06 wt. %of carbamate initiator. All the ingredients except the initiator wereweighed into a 20 ml vial. The vial was capped and the mixture shakenuntil visually homogenous. The dormant carbamate initiator was thenweighed into the mixture. The final mixture was capped and shaken for 30seconds, and then applied over the dried color coat using a 3 mil Birdtype film applicator.

Commercial systems: the commercial systems were applied in a similarmanner also on vitronail substrate panels and cured as per instructionsand procedures common to the industry.

The various coats of the nail coating systems are summarized in table 9.

TABLE 9 Nail polish system Base coat Color coat Top coat Inventive 7.1Base coat A Color coat A Top coat A Inventive 7.2 Base coat B Color coatA Top coat B UV nail gel OPT GelColor OPT GelColor OPT GelColor Basecoat Pink Flamenco Top coat Color coat Conventional Revlon ColorStayNina Ultra Pro Revlon Colorstay nail polish Gel-Smooth Mariachi Gel EnvyDiamond Base coat Color coat Top Coat

Nail polish performance test results are shown in the table 10.Inventive coatings 7.1 and 7.2 exhibit comparable gloss and tack freedry times compared to the commercial references. The pencil hardness ofthese coatings are substantially greater than either of the referencesused in this testing. The acetone removal times of both inventivecoatings were significantly faster than the commercial UV nail gelcoating system. The conventional nail polish system was easiest toremove as expected, but the film was also extremely soft.

TABLE 10 Tack free time individual coat Performance whole system ColorAcetone Base coat coat Top coat Pencil removal Nail polish system (min)(min) (min) 60° gloss hardness time (min) Inventive 6.1 3 3.5 5.5 756.5H 13 Inventive 6.2 2.3 3.8 5.3 72 8H 20 UV nail gel 4 3.5 3.5 73 3.5H27 Conventional nail 1.25 2.5 1.3 81 9B 0.5 polish

Inventive Example 8

The dormant carbamate initiator was used to cure a mixture of theacetoacetate modified polyol of example 10 and DTMPTA. A vial wascharged with 46 wt. % acetoacetate modified polyol, 0.74 wt. % alkylethoxylate wetting agent, 36.86 wt. % DTMPTA and 9.2 wt. % BA. The vialwas stirred until homogenous. Next, a carbamate initiator type II wasprepared as in example 3 (46% in ethanol) and 7.4 wt. % of thisinitiator was then weighed into the coating mixture. The final mixturewas capped and shaken for 30 seconds, and applied on a polycarbonatesheet using a 3 mil Bird type film applicator. The resulting coatingcured quickly and was tack free in 20 minutes and had a glossyappearance (94 at 60°) and the gel time was 65 minutes.

As control, 45.87 wt. % of the STEPANPOL® PC-2011-225 polyol resin, 0.69wt. % EFKA SL-3288; and 18.35 wt. % BA were weighed into a 20 ml vialand mixed. Next, 34.40% Basonat HB 100 isocyanate curative was added andthe mixture stirred again before 0.69 wt. % Borchi-Kat 24 urethanecatalyst was added and stirred in. A film was drawn down using a 3 milBird bar type film applicator. The resulting glossy coating (93 at 60°)cured tack free in 50 minutes but the gel time was only 2 minutes.

Inventive Example 9

Dormant carbamate initiator type II was prepared in example 3 from TBAOH in ethanol and varying amounts of this initiator system was used toassess cure speed using the malonate resin prepared under example 6 andTMPTA. The molar ratio for malonate methylene CH₂ to TMPTA was fixed at3:2, while the ethanol content was kept as constant as possible at about10 wt. % of the final formulation. The amount of initiator used isexpressed as mole percent relative to the number of protons that can beabstracted to form activated Michael donor species. Films were appliedon glass substrates to test tack free time and these are summarized intable 11. Some of the films with higher initiator concentrations gave awrinkled appearance as the solvent content/package was not optimal inview of such fast cure speeds, however, increased carbamate initiatorcontent provided faster cure rates.

TABLE 11 Carbamate initiator (mol %) 0.83 1.67 3.33 6.67 10 13.33 Tackfree time 600 455 328 213 154 100 (sec)

Inventive Example 10

Carbamate initiator solutions where prepared as in example 4, butvarying amounts of excess DMA DMC were employed in the synthesisprocedure. A series of TBMA DMC initiator solutions with increasingamounts of excess DMA DMC was thus obtained and evaluated for efficacyas dormant carbamate initiator. In a general evaluation procedure, 2.0 gof malonate resin V of example 11 was mixed with 2.276 g of DTMPTA, 0.4g of BA and about 0.67 g of the TBMA DMC initiator solution was added.The complete formulation was mixed well and then a 6 mil test film wasapplied on a polycarbonate substrate to test the curing behavior.Similar formulations were prepared to evaluate tack free time and geltime with results for the various TBMA DMC/DMADMC ratios shown in Table12. Formulations with increasing amounts of excess DMA DMC show longergel times, but the tack free time remains essentially the same.

TABLE 12 TBMA DMCC Tack free time (mmol) DMA DMC (mmol) (min) Gel time(hour) 0.66 0.00 4 13 0.66 0.07 4 13 0.66 0.20 4 37 0.66 0.33 4 50 0.660.66 4 109

Similar coating formulations were employed to evaluate carbamatematerials in various combinations. Isobutylammonium isobutylcarbamate(IBA IBC) was made by first dissolving 25 g of isobutylamine in 25 g ofdichloromethane. CO₂ gas was passed through this solution and thereaction progress was followed for IBA IBC formation by NMR. The IBA IBCwas obtained as a solid on dichloromethane and potentially amine waslost in the CO₂ flow with NMR confirming IBA IBC purity. Titrations werecarried out to determine the acid/amine values and equivalent molecularwt. of the synthesized IBA IBC. Similar as in example 10, TBMA ethoxidein ethanol was prepared and mixed with IBA IBC to prepare a solution oftributylmethylammonium isobutylcarbamate (TBMA IBC). Tack free time andgel time results for the various carbamate combinations are shown inTable 13.

TABLE 13 TBMA Tack Gel DMC DMA DMC IBA IBC TBMA IBC free time time mmolmmol mmol mmol (min) (hour) 0.44 0.22 0 0 5 37 0.43 0 0.21 0 14 87 0 00.28 0.45 30 105

Inventive Example 11

Unsubstituted and substituted malonate resins VI, VII and VIII ofexamples 12, 13 and 14 respectively, were each tested in a simplecoating formulation of resin, DTMPTA crosslinker, BA solvent and adormant initiator as prepared via example 4. All materials are mixedusing a laboratory vortex mixer to create a homogeneous solution. Vialsare prepared to observe gel time and 6 mil thick films are drawn onpolycarbonate test panels to assess tack free time. Results arepresented in Table 14. The substituted malonate resins show much longergel times in comparison to the unsubstituted malonate resin while thecure speed determined in terms of tack free time remains veryacceptable.

TABLE 14 Initiator Resin DTMPTA BA solution* Tack free Gel time Resintype (g) (g) (g) (g) time (min) (days) VI 1 1.08 0.3 0.3 2 overnight VI1 0.54 0.3 0.3 3 overnight VII 1 0.51 0.3 0.3 3  9 VIII 1 0.48 0.3 0.3 423 *Initiator solution contains 28.1 wt. % dormant initiator

Inventive Example 12

Model clear coat formulations were prepared with resin IX, X, XI or XIIof examples 15, 16, 17 or 18 respectively, and DTMPTA and/or the DUDAcrosslinker of example 19. A 1 to 1 molar ratio of active malonatemethylene hydrogen to acrylate was maintained in the formulations and 10wt. % of both BA solvent and dormant initiator solution as prepared viaexample 4 was added to the coating mixture. Vials were prepared toobserve gel time and 3 mil thick films were drawn on aluminum testpanels test panels to assess tack free time and mechanical properties.An OPI GelColor Top Coat commercial system was used as control referenceand a 3 mil thick coating was applied and cured as per instructions andprocedures common to the UV/LED nail gel industry. Results are presentedin Table 15.

TABLE 15 Tack DTMPTA DUDA free Resin acrylate acrylate time PencilConical Reverse Direct Water system mol % mol % (min) Hardness mandrelImpact Impact Blush OPI top na* na* nm* HB 100% 31% 22% Pass coat IX 0100 7 9H 100% 31% 41% Pass IX 30 70 3 8H 100% 19% 38% Pass X 0 100 8 9H100% 63% 34% Pass X 100 0 4 8H 32% 19% 34% Fail XI 100 0 4 8H 100% 22%44% Fail XI 0 100 5 4H 100% 47% 44% Pass XII 90 10 4 6H 58% 25% 31% PassXII 50 50 3 9H 100% 22% 47% Pass XII 0 100 4 9H 100% 53% 69% Pass na*:not applicable/ nm*: not measured

Inventive Example 13

An inventive nail polish system was formulated as a two coat system (aColorcoat and a Top Clearcoat), where the Colorcoat was applied directlyon the bare nail surface, and then finished with the Top Clearcoat. Twopigment dispersions were prepared first, prior to formulating the colorcoat.

Preparation of an iron oxide blue pigment dispersion: 200 g of a resinas prepared under example 18 (resin XII) was weighed into a 500 mljacketed mixing pot. The mixing pot was placed under a Dispermat highspeed mixer equipped with 60 mm dual nylon disk pearl mill mixerattachment from BYK Instruments. The disk was lowered into the mixingpot to about 10 mm from the inside bottom of the pot. A water bath setto 140° F. was connected to the jacketed pot, and mixing was started at500 rpm. Blue iron oxide powder (60 g; SunChroma Iron Blue supplied bySun Chemical) was slowly poured into the pot while it was mixed. Then,350 g of milling media were added to the pot. The milling media was0.7-0.9 mm Yttria stabilized zirconium oxide beads supplied by NorstoneInc. The pot was covered, and the mixing speed was increased to 2500 rpmand maintained for 4 hrs. At the end of this time, the mixing wasstopped. The contents of the mix pot were poured through a 190 micronGerson paint filter screen (supplied by Gardco), in order to remove thebeads. The final pigment dispersion was dark blue and was found to havea Hegman Fineness of Grind value of 7. The total net yield of thisprocess was 57.5%.

Preparation of a titanium oxide white pigment dispersion: The sameprocedure as described for the iron oxide blue dispersion was used hereusing 200 g of a resin as prepared under example 18 (resin XII); 86 gtitanium dioxide (TiO₂; supplied by Making Cosmetics); 350 g millingbeads. Mixing/milling was performed at 140° F. at 2500 rpm for 4 hours,followed by filtering out the milling beads. A Hegman Grind of 7 wasdetermined and the net yield of the white pigment dispersion from theprocedure was 79%.

Colorcoat preparation: A blue Colorcoat was prepared as follows: into a20 ml glass vial, 0.23 g of the above blue pigment dispersion and 0.54 gof the white pigment dispersion were added. An additional 0.56 g of aresin as prepared under example 18 (resin XII) was added to the vial. Astoichiometric excess of the crosslinker as prepared in example 19 wasadded, 3.5 g of DUDA, and solvent (0.68 g of n-butyl acetate) was addedto the vial as well. The mixture was stirred by hand using a small metalspatula and the vial was capped. When time for the film applicationarrived, 0.48 g of dormant carbamate initiator as prepared under example4 was added vial and the mixture was stirred using a spatula and thenapplied. Total mixing time was 1-2 min.

Top Clearcoat preparation: Into a 20 ml glass vial were weighed thefollowing ingredients: 1.9 g of an unpigmented resin as prepared underexample 18 (resin XII); 1.4 g of DUDA crosslinker as prepared underexample 19, 1.7 g of DTMPTA crosslinker, 0.4 g BA, 0.06 g BD asanti-wrinkling additive, and 0.25 g of Polytex NX-55 gloss additive(supplied by Estron Chemical). The mixture was stirred by hand using asmall metal spatula and the vial was capped. At the time of filmapplication, 0.70 g of dormant carbamate initiator of Example 4 wasadded to the vial and the mixture was stirred using a spatula and thenapplied. Total mixing time was 1-2 min.

Inventive nail polish system (Colorcoat and Top Clearcoat) filmapplication and testing: A 3 mil wet film of the Colorcoat was appliedon aluminum and polycarbonate test panels. The films were allowed to airdry for 9-11 min prior to application of the Top Clearcoat over thedried Colorcoat film. The films were allowed to sit at ambientlaboratory conditions overnight before evaluating their physicalproperties.

A commercial UV nail gel system (OPI GelColor) was used as comparison.The system consists of a base, color and top coat. The base coat wasfirst applied and cured prior to application and curing of the OPIGelColor color coat, which was followed by application and curing of theOPI GelColor Top coat. The GelColor applications instructions werefollowed as closely as possible. All films were applied at a 3 mil wetfilm thickness and the system was allowed to equilibrate overnightbefore evaluation.

Performance results for the inventive and reference systems are shown inTable 16.

TABLE 16 Nail Pencil Acetone polish Gloss Hard- Conical Reverse DirectWater removal system 60° ness mandrel Impact Impact Blush (min) Inven-85 3H 100% 38% 34% Pass 16 tive OPI 83 3H 100% 6% 13% Pass >20 control

Inventive Example 14

FD&C and D&C dyes commonly used in nail polish and gel formulations wereevaluated in Michael addition based crosslinkable compositions. Suchcolorants may also be used in other coating application industries suchas automotive and industrial paints, architectural paints, plastics,adhesives and others. Concentrated dispersions of dye in malonate resinXIII from example 20 were prepared first. Said dispersions were thenused to formulate simple color coat formulations. All color coats wereformulated to generate specific comparative dye concentrations at 1% and3% dye loading by weight. The amounts of raw materials added to thecoating formulation are adjusted to achieve this desired dye loading.Finally, coatings of controlled thickness are prepared to evaluatecertain applications and color properties. The following are specificexamples how a dye dispersion and the color coat are prepared and serveas general preparative example:

Dye dispersion: First, 10.04 g of malonate resin XIII from example 20was weighed directly into a tared 60 ml capacity mortar and 3.00 g ofD&C Red 30 dye was weighed in next. A spatula was briefly used to handblend the dye into the resin and a pestle was then used to grind thepaste in the mortar to a fine consistency. The mixture was ground/milledby hand for approximately 10-25 minutes using the pestle and mortaruntil a Hegman Fineness of Grind value of 7 was achieved. The pigmentdispersion was then transferred to a glass jar and sealed for later use.

Color coat: Into a 20 ml glass vial, 0.65 g of the above D&C Red 30 dyedispersion was added. An additional 1.95 g of the malonate resin XIIIfrom example 20 was charged to the vial and 1.58 g of DTMPTA was addednext. The materials in the vial were mixed by hand using a spatula toachieve homogeneity. After this, 0.41 g of BA was mixed in as well. Thevial was sealed and vigorously shaken until homogenous. Test panels tobe coated were placed into position at this point. Bird Bars (3 & 6 mil)for coating application were made ready. The glass vial was unsealed and0.41 g of dormant carbamate initiator of example 4 is added. The lid wasplaced back on the vial. The complete mixture was vigorously shaken for1-3 minutes to make it homogenous. Once mixing was completed, themixture was promptly cast as films using the Bird Bars on 4″×6″polycarbonate panels. Tack free time was recorded and coating surfacewrinkling was observed as the films cured. Decorative coatings appliedon finger- and/or toe nails typically are about 1.0-1.5 mil thick,sometimes up to 2 mil thick per coating layer when applied by brushalthough even thicker coatings are applied by consumers that are lessexperienced.

Various dyes were thus evaluated and compared to a dye free (uncolored)control and results are shown in Table 17. The uncolored coating (usedas a reference film) exhibits slight surface wrinkling, in the absenceof dye. The amount of surface wrinkling is inherent in the resin/formulacombination used for this evaluation. Any worsening of this surfacewrinkling is considered less desirable.

TABLE 17 Films - 3 mils Films - 6 mils applied applied thicknessthickness Tack Tack Dye free Coating free Coating D&C or FD&C Conc timesurface time surface dye name Supplier (by wt.) (min) wrinkling (min)wrinkling Blank Control no dye used no dye 1.7 slight 2.0 slight presentAnnatto Sensient Technolgy Corp. 1% 1.4 none 2.0 none Annatto SensientTechnolgy Corp. 3% 2.0 none 2.7 slight Beta-Carotene Sensient TechnolgyCorp. 1% 1.5 none 2.0 very slight Beta-Carotene Sensient Technolgy Corp.3% 1.8 none 2.0 very slight Black 2 MakingCosmetics Inc. 1% 1.5 none 2.2severe Black 2 MakingCosmetics Inc. 3% 4.4 slight 8.5 severe Blue 1Emerald Performance 1% 1.6 none 2.3 very slight Materials Blue 1 EmeraldPerformance 3% 2.3 none 3.3 slight Materials Blue 2 Spectra Colors Corp.1% 1.1 none 2.1 none Blue 2 Spectra Colors Corp. 3% 1.7 slight 3.0slight Brown 1 Sensient Technolgy Corp. 1% 1.8 slight 3.4 slight Brown 1Sensient Technolgy Corp. 3% 3.0 slight 3.8 severe Caramel SensientTechnolgy Corp. 1% 1.5 very slight 2.0 very slight Caramel SensientTechnolgy Corp. 3% 1.4 very slight 2.0 very slight Carmine Red EmeraldPerformance 1% 2.5 none 3.5 very slight Materials Carmine Red EmeraldPerformance 3% 1.3 very slight 2.0 very slight Materials Green 3 SpectraColors Corp. 1% 1.9 none 2.1 slight Green 3 Spectra Colors Corp. 3% 2.1none 2.9 slight Green 5 Spectra Colors Corp. 1% 2.0 none 2.5 none Green5 Spectra Colors Corp. 3% 3.8 none 3.0 slight Green 6 Spectra ColorsCorp. 1% 1.7 none 2.2 very slight Green 6 Spectra Colors Corp. 3% 2.1slight 2.7 slight Orange 4 Spectra Colors Corp. 1% 3.7 none 4.3 veryslight Orange 4 Spectra Colors Corp. 3% 7.0 slight 9.2 severe Red 21Spectra Colors Corp. 1% 2.3 none 3.3 slight Red 21 Spectra Colors Corp.3% 3.2 none 4.3 none Red 22 Emerald Performance 1% 3.0 none 3.0 slightMaterials Red 22 Emerald Performance 3% 5.3 none 5.5 severe MaterialsRed 27 Spectra Colors Corp. 1% 2.3 none 3.5 slight Red 27 Spectra ColorsCorp. 3% 2.4 slight 4.3 slight Red 28 Emerald Performance 1% 2.8 slight4.0 slight Materials Red 28 Emerald Performance 3% 3.3 slight 5.3 severeMaterials Red 30 Spectra Colors Corp. 1% 1.8 slight 2.2 slight Red 30Spectra Colors Corp. 3% 2.0 none 2.8 slight Red 33 Emerald Performance1% 2.3 none 3.0 slight Materials Red 33 Emerald Performance 3% 3.1slight 4.2 slight Materials Red 34 Sentient Cosmetics Tech. 1% 1.8 none3.3 slight Red 34 Sentient Cosmetics Tech. 3% 2.3 slight 5.5 severe Red36 Spectra Colors Corp. 1% 2.3 none 3.9 none Red 36 Spectra Colors Corp.3% 3.0 none 4.5 very slight Red 4 Spectra 1% 3.2 very slight 6.8 severeRed 4 Spectra Colors Corp. 3% 18.0 slight 30.0 severe Red 40 SpectraColors Corp. 1% 2.2 slight 3.1 slight Red 40 Spectra Colors Corp. 3% 3.8slight 4.3 slight Red 6 Spectra Colors Corp. 1% 2.0 slight 2.7 none Red6 Spectra Colors Corp. 3% 2.0 slight 2.6 none Red 7 Spectra Colors Corp.1% 2.0 slight 2.9 slight Red 7 Spectra Colors Corp. 3% 2.5 slight 5.4severe Violet 2 Emerald Performance 1% 1.6 none 2.2 very slightMaterials Violet 2 Emerald Performance 3% 2.5 none 3.2 very slightMaterials Yellow 10 Spectra Colors Corp. 1% 2.5 none 4.3 very slightYellow 10 Spectra Colors Corp. 3% 3.3 none 9.0 very slight Yellow 11Spectra Colors Corp. 1% 2.0 none 2.2 very slight Yellow 11 SpectraColors Corp. 3% 2.5 none 3.5 very slight Yellow 5 Spectra Colors Corp.1% 2.0 none 2.9 slight Yellow 5 Spectra Colors Corp. 3% 2.5 slight 3.4slight Yellow 6 Spectra Colors Corp. 1% 2.2 none 2.8 very slight Yellow6 Spectra Colors Corp. 3% 3.3 slight 4.0 slight

The films prepared at 3% dye concentration and 3 mil film wet appliedfilm thickness, were additionally evaluated by color spectrophotometryto monitor color change upon aging. Once the applied coating became tackfree, a timer was started. Color measurements were carried out for eachfilm. Each coated panel was measured at 3 different points during theaging process: (1) 1 hr.; (2) overnight (>16 hrs); and (3) after 1 week.Color analyses were performed using a calibrated DataColor 800Spectrophotometer to measure the coated panels. The panels sat inambient laboratory conditions during the period of aging. The colormeasurement changes (delta values for a, b, 1, and the total colorchange ΔE, CIELAB system) for overnight and 1 week of aging weredetermined using the one hour color measurement as the reference pointfrom which the instrument's software calculated the delta values.Whether a color change is noticeable to the eye is a matter of personalopinion for end users of nail color cosmetics. For purposes of thisexample, color changes of ΔE of <=1.0 were interpreted as Good. Colorchange of ΔE>1.0 but <=2.0 were interpreted as Fair yet still consideredacceptable as being viewed that such a color change would be likelydetected by a trained eye only. Color changes of ΔE>2.0 were lessdesirable as this color change is likely to be readily noticeable evento an untrained eye. A color change ΔE>4.0 is significant, while a colorchange of ΔE>5 is an entirely different color. Table 18 shows resultsfor the color measurements.

TABLE 18 Films - 3 mils applied thickness Same day color analysis(reference point) Overnight color change analysis One week color changeanalysis L* Lightness a* b* ΔE* ΔE dye 0 = Black +Red +Yellow totalcolor total color name 100 = White −Green −Blue ΔL* Δa* Δb* differenceΔL* Δa* Δb* difference Annatto 51.65 25.71 49.80 −0.59 1.43 −0.91 1.80−0.54 0.86 −1.62 1.91 Beta-Carotene 48.85 19.12 24.38 −1.93 2.32 −2.123.69 1.36 −3.69 −1.37 4.17 Black 2 22.83 −0.01 −0.48 0.92 −0.02 0.090.93 1.00 −9.05 −0.04 1.00 Blue 1 29.59 13.41 −7.86 4.18 −8.57 11.3914.86 13.23 1.56 23.72 27.21 Blue 2 23.77 4.08 −7.06 1.44 5.20 −11.3412.56 17.90 −3.11 −4.92 18.83 Brown 1 36.11 37.55 21.69 1.03 −0.29 0.961.43 2.42 −2.54 −0.18 3.51 Caramel 56.59 3.37 10.06 −0.2 0.09 0.29 0.36−0.83 0.28 0.92 1.27 Carmine Red 37.16 25.48 1.61 −0.6 −1.01 −0.02 1.18−2.46 −1.94 0.26 3.14 Green 3 23.79 4.86 −8.46 1.26 3.84 −9.04 9.9022.05 −5.3 −0.3 22.69 Green 5 24.68 −5.2 −0.67 0.70 0.37 −0.82 1.14 1.111.01 −0.33 1.53 Green 6 26.01 −2.17 −2.64 0.26 0.55 0.38 0.71 2.10 −1.46−0.86 2.70 Orange 4 30.78 25.29 11.78 −0.53 −2.20 −2.6 3.45 4.85 4.846.40 9.37 Red 21 47.23 43.19 30.33 0.52 −0.07 1.01 1.14 1.61 −1.26 3.524.07 Red 22 46.02 42.46 27.99 0.20 −0.10 0.51 0.56 3.09 −0.14 6.43 7.14Red 27 40.26 48.65 10.09 0.47 −0.03 1.03 1.14 −0.8 3.29 0.00 3.39 Red 2840.56 49.28 11.65 0.68 0.13 1.17 1.36 0.36 3.31 1.21 3.57 Red 30 33.3430.65 13.84 −0.34 −0.42 0.05 0.48 0.24 −0.79 −0.44 0.93 Red 33 24.598.76 2.10 0.34 0.34 0.22 0.53 0.73 0.84 0.93 1.25 Red 34 27.26 16.756.34 −0.03 0.20 −0.13 0.23 4.77 1.86 5.12 5.22 Red 4 35.70 29.05 20.44−0.87 −4.02 −0.79 4.19 −3.03 0.75 −5.47 6.30 Red 40 27.58 20.78 7.241.47 −1.75 −0.61 2.37 8.66 5.63 10.12 10.83 Red 6 40.92 39.03 29.31−0.49 −2.85 −0.09 2.89 −2.03 −4.16 −5.55 7.23 Red 7 33.01 31.58 16.730.17 1.88 0.40 1.93 2.15 1.44 1.98 3.26 Violet 2 25.09 5.12 −1.48 −1.130.35 −0.83 1.44 3.58 −0.22 −4.47 5.73 Yellow 10 56.22 7.70 51.62 0.86−0.88 −3.35 3.57 0.15 −0.32 −3.76 3.77 Yellow 11 61.10 1.84 57.23 −0.06−1.53 −1.7 2.29 0.43 −3.38 −3.7 5.03 Yellow 5 54.80 14.19 53.08 −0.13−0.07 −0.25 0.29 −0.43 0.03 −1.64 1.70 Yellow 6 33.05 17.16 5.73 1.223.34 1.94 4.05 3.19 5.37 3.01 7.37

Inventive Example 15

FD&C and D&C approved pigments commonly used in nail polish and gelformulations were evaluated in Michael addition based crosslinkablecompositions. Such colorants may also be used in other industries suchas automotive and industrial paints, architectural paints, plastics,adhesives and others. Concentrated dispersions of pigment in malonateresin XIII from example 20 were prepared first in a similar manner asdescribed for the dye dispersion in the inventive example 14 above. Saiddispersions were then used to formulate simple color coat formulations.All color coats were formulated to generate specific comparative pigmentconcentrations at 3% pigment loading by weight. The amounts of rawmaterials added to the coating formulation are adjusted to achieve thisdesired pigment loading. Finally, coatings of controlled thickness areprepared to evaluate certain applications and color properties. Thefollowing is an example how a pigment dispersion and color coat isprepared and serves as a general preparative example: A 40% concentratedispersion of Chromium Oxide Green pigment in malonate resin XIII fromexample 20 was prepared by means of grinding the pigment in the resinwith a mortar and pestle until the paste showed a Hegman Fineness ofGrind value of 7. To prepare the coating formulation, 0.38 g of the 40%Chromium Oxide Green dispersion was combined with 2.23 g of malonateresin XIII from example 20, and 1.58 g of DTMPTA, mixed and then 0.41 gof BA was added to dilute prior to adding 0.41 g of dormant carbamateinitiator of example 4. The complete mixture was vigorously shaken tomake it homogenous. Once mixing was completed, the coating mixture waspromptly applied as a film to polycarbonate substrate panels. Films werecast at 3 and 6 mil wet thickness and evaluated for tack free time,surface wrinkling and overnight color fading. Coating surface wrinklingand overnight color fading are visual observations about the surfaceroughness and change of initial color after sitting overnight. The geltime and brushability time were also determined for the mixture.Acceptable tack free times with reasonable brushability and gel timesare achieved, while color fading was also deemed acceptable. Results aresummarized in Table 19.

TABLE 19 Films - 3 mils Films - 6 mils applied thickness appliedthickness Tack Tack Brushability Gel free Coating Overnight free CoatingOvernight Pigment time time time surface color time surface colordescription Supplier (hours) (hours) (min) wrinkling fading (min)wrinkling fading Blank control n/a 3.3 >6 1.5 none n/a 2.2 slight n/a(unpigmented) 3% Aluminum Altana AG <0.5 0.5 2.0 none none 3.0 none nonePowder 3% Bismuth BASF SE >1.0 >1 1.7 slight none 2.5 slight noneOxychloride 3% Black Iron MakingCos >1.0 >1 1.5 none none 1.8 none noneOxide metics Inc. 3% Brown Iron MakingCos 5.0 >8 1.7 slight none 2.8moderate none oxide metics Inc. 3% Chromium MakingCos 5.0 >8 1.7 slightnone 2.1 moderate none Oxide Green metics Inc. 3% Iron Blue Sun 5.0 >81.5 slight none 2.1 moderate none (Ferric Ferrocyanide Chemical Blue)Corp. 3% Manganese Sun >1.0 >1 1.3 none none 2.0 slight none VioletChemical Corp. 3% Mica MakingCosmetics 1.0 >1 1.4 none none 2.0 nonenone Inc. 3% Red Iron Oxide MakingCosmetics 2.3 >5 1.8 none none 2.8slight none Inc. 3% Titanium Sun 5.0 >8 1.8 none none 2.5 moderate noneDioxide Chemical Corp. 3% Ultramarine Ferro Corp. >1.0 >1 1.8 noneslight 2.7 slight slight Blue 3% Ultramarine Ferro Corp. >1.0 >1 2.0none slight 2.5 none slight Pink 3% Ultramarine Ferro Corp. >1.0 >1 1.8none none 2.5 slight none Violet 3% Yellow Iron Sun 2.0 >3 2.0 severenone 4.7 severe none Oxide Chemical Corp.

LIST OF CHEMICAL ACRONYMS USED IN THE EXAMPLES

-   BA butyl acetate-   BD 1,3-butanediol-   EA ethyl acetate-   DEG diethylene glycol-   DEGMEE diethylene glycol monoethylether-   DEEM diethyl ethylmalonate-   DEM diethyl malonate-   DEMM diethyl methylmalonate-   DEtC diethyl carbonate-   DMA DMC dimethylammonium dimethylcarbamate-   DMeC dimethylcarbonate-   DTMPTA di-trimethylolpropane tetraacrylate-   DUDA diurethane diacrylate-   EtOH ethanol-   Gly glycerol-   HCl hydrochloric acid-   HD 1,6-hexanediol-   HEA 2-hydroxyethyl acrylate-   IBA IBC isobutylammonium isobutylcarbamate-   PD 1,3-propanediol-   PEG 300 polyethylene glycol, Mw=300-   tBAA tert-butyl acetoacetate-   TBA DMC tetrabutylammonium dimethylcarbamate-   TBA OH tetrabutylammonium hydroxide-   TBMA tributylmethylammonium-   TBMA Cl tributylmethylammonium chloride-   TBMA DMC tributylmethylammonium dimethylcarbamate-   TBMA IBC tributylmethylammonium isobutylcarbamate-   THF tetrahydrofuran-   TMDI trimethylhexamethylene diisocyanate-   TMP trimethylolpropane-   TMPTA trimethylolpropane triacrylate

The present disclosure may be embodied in other specific forms withoutdeparting from the spirit or essential attributes of the invention.Accordingly, reference should be made to the appended claims, ratherthan the foregoing specification, as indicating the scope of thedisclosure. Although the foregoing description is directed to thepreferred embodiments of the disclosure, it is noted that othervariations and modification will be apparent to those skilled in theart, and may be made without departing from the spirit or scope of thedisclosure.

1. A crosslinkable coating composition comprising: ingredient A that has at least two protons that can be activated to form a Michael carbanion donor; ingredient B that functions as a Michael acceptor having at least two ethylenically unsaturated functionalities each activated by an electron-withdrawing group; and a dormant carbamate initiator of Formula (1)

wherein R₁ and R₂ can be independently selected from hydrogen, a linear or branched substituted or unsubstituted alkyl group having 1 to 22 carbon atoms; 1 to 8 carbon atoms; or 1 to 4 carbon atoms; and A^(n+) is a cationic species or polymer and n is an integer equal or greater than 1 with the proviso that A^(n+) is not an acidic hydrogen; and optionally further comprising ammonium carbamate (H₂NR₁R₂ ⁺⁻OC═ONR₁R₂).
 2. The crosslinkable coating composition according to claim 1, wherein the ingredient A is independently selected from a malonate group containing compound, a malonate group containing oligomer, a malonate group containing polymer, an acetoacetate group containing compound, an acetoacetate group containing oligomer, an acetoacetate group containing polymer or combinations thereof.
 3. The crosslinkable coating composition according to claim 2, wherein the malonate group containing compound, malonate group containing oligomer, malonate group containing polymer, an acetoacetate group containing compound, acetoacetate group containing oligomer, or acetoacetate group containing polymer are each selected from the group consisting of: polyurethanes, polyesters, polyacrylates, epoxy polymers, polyamides, polyesteramides or polyvinyl polymers, wherein such compounds, oligomers or polymers have (i) a malonate group, (ii) an acetoacetate group or (iii) combinations thereof located in a main chain of such compound or oligomer or polymer or a side chain of such compound or oligomer or polymer.
 4. The crosslinkable coating composition according to claim 3, wherein ingredient B is selected from the group consisting of acrylates, fumarates, maleates and combinations thereof.
 5. The crosslinkable coating composition according to claim 4, wherein the acrylate is independently selected from the group consisting of hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, di-trimethylolpropane tetraacrylate, bis(2-hydroxyethyl acrylate) trimethylhexyl dicarbamate, bis(2-hydroxyethyl acrylate), 1,3,3-trimethylcyclohexyl dicarbamate, bis(2-hydroxyethyl acrylate) methylene dicyclohexyl dicarbamate and combinations thereof.
 6. The crosslinkable coating composition according to claim 4, wherein ingredient B is independently selected from the group consisting of polyesters, polyurethanes, polyethers and/or alkyd resins each containing at least two pendant ethylenically unsaturated groups each activated by an electron-withdrawing group.
 7. The crosslinkable coating composition according to claim 4, wherein ingredient B is independently selected from the group consisting of polyesters, polyurethanes, polyethers and/or alkyd resins each containing at least one pendant acryloyl functional group.
 8. The crosslinkable coating composition according to claim 4, further comprising an ingredient D having one or more reactive protons that are more acidic than the protons of ingredient A, with respect to pKa and/or less acidic than the ammonium cation of the optional ammonium carbamate, with respect to pKa.
 9. The crosslinkable coating composition according to claim 4, further comprising less than 10 wt. %; 5 wt. %; 1 wt. %; 0.1 wt. %; 0.01 wt. % water.
 10. The crosslinkable coating composition according to claim 4, being substantially free of water.
 11. The crosslinkable coating composition according to claim 1, further comprising an organic solvent.
 12. The crosslinkable coating composition according to claim 11, wherein the organic solvent is independently selected from the group consisting of an alcohol, ester, ether, glycol ether, ketone, aromatic and combinations thereof.
 13. The crosslinkable coating composition according to claim 12, wherein the alcohol is independently selected from the group consisting of methanol, ethanol, iso-propanol, butanol, iso-butanol and combinations thereof.
 14. The crosslinkable coating composition according to claim 1, wherein A^(+n) is a monovalent quaternary ammonium compound of Formula (2)

wherein R₃, R₄ and R₅ are independently selected from linear or branched alkyl chains having from 1 to 22 carbon atoms; or 1 to 8 carbon atoms and combinations thereof; and wherein R₆ is independently selected from the group consisting of: methyl, an alkyl group having from 2 to 6 carbon atoms or a benzyl group.
 15. The crosslinkable coating composition according to claim 1, wherein the dormant carbamate initiator initiates Michael Addition to achieve cross linking when the crosslinkable coating composition is applied to a surface.
 16. The crosslinkable coating composition according to claim 1, wherein ingredient A, ingredient B and the carbamate salt are contained in a container having two or more chambers, which are separated from one another.
 17. The crosslinkable coating composition according to claim 16, wherein ingredient A and ingredient B are contained in separate chambers to inhibit any reaction.
 18. The crosslinkable coating composition according to claim 16, wherein the carbamate initiator is contained in the chamber having ingredient A, and optionally containing CO₂ and/or ammonium carbamate.
 19. The crosslinkable coating composition according to claim 16, wherein ingredient A and ingredient B are contained in the same chamber and the carbamate initiator is contained in a separate chamber to inhibit any reaction and said separate chamber optionally containing CO₂ and/or ammonium carbamate.
 20. The crosslinkable coating composition according to claim 1 wherein ingredient A and ingredient B and carbamate initiator are contained in a container having a single chamber, wherein the container optionally independently (i) contains CO₂ and/or ammonium carbamate or (ii) contains ammonium carbonate and is filled to capacity with essentially no space remaining for other solid, liquid or gaseous ingredients.
 21. A polymerizable nail coating composition comprising the crosslinkable coating composition according to claim
 1. 22. The polymerizable nail coating composition according to claim 21, further comprising at least one solvent selected from the group consisting of acetone, ethyl acetate, butyl acetate, isopropyl alcohol, ethanol, methylethyl ketone, and combinations thereof.
 23. The polymerizable nail coating composition according to claim 21, further comprising one or more of dyes, pigments, effect pigments, phosphorescent pigments, flakes and fillers and combinations thereof.
 24. The polymerizable nail coating composition according to claim 21, further comprising a rheological additive to modify rheology.
 25. The polymerizable nail coating composition according to claim 21, further comprising a wetting agent.
 26. The polymerizable nail coating composition according to claim 21, further comprising an adhesion promotor.
 27. The polymerizable nail coating composition according to claim 21 further comprising nitrocellulose, polyvinylbutyral, tosylamide formaldehyde and/or tosylamide epoxy resins.
 28. The polymerizable nail coating composition according to claim 21, further comprising a cellulose acetate alkylate selected from the group consisting of cellulose acetate butyrate, cellulose acetate propionate, and mixtures thereof.
 29. The polymerizable nail coating composition according to claim 21, further comprising at least one colorant independently selected from the group consisting of (i) a dye; (ii) an inorganic pigment; (iii) a lake or (iv) combinations thereof.
 30. The polymerizable nail coating composition according to claim 29, wherein the dye is selected from the group consisting of D&C Red No. 30, D&C Red No. 33, D&C Black No. 2, D&C Yellow No. 5, D&C Green No. 5, Annatto and Caramel.
 31. The polymerizable nail coating composition according to claim 29, wherein the inorganic pigment is selected from the group consisting of red iron oxide; yellow iron oxide; titanium dioxide; brown iron oxide; chromium oxide green; iron blue (ferric ferrocyanide blue); ultramarine blue; ultramarine violet; ultramarine pink; black iron oxide; bismuth oxychloride; aluminum powder; manganese violet; mica; bronze powder; copper powder; guanine and combinations thereof.
 32. The polymerizable nail coating composition according to claim 29, wherein the lake is a D&C lake.
 33. A coating composition comprising the crosslinkable coating composition according to claim
 1. 34. A crosslinkable coating composition comprising: ingredient A that has at least two protons that can be activated to form a Michael carbanion donor; ingredient B that functions as a Michael acceptor having at least two ethylenically unsaturated functionalities each activated by an electron-withdrawing group; and ingredient C, which is a dormant carbamate initiator system formed from: a: ammonium carbamate salt derived from the reaction of: a1: carbon dioxide a2: one or more polyamines a3: optionally one or more monoamines b: such ammonium carbamate salt being subsequently treated with base, ion exchange or other chemical means so that at least part of the protonated ammonium cations have been replaced by A^(n+), and where A^(n+) is a cationic species or polymer and n is an integer equal or greater than 1 with the proviso that A^(n+) is not an acidic hydrogen. 